IDW48-2015 See Program - inorganic discussion weekend

Transcription

48th Inorganic Discussion Weekend
48e Rencontres inorganiques
November 6-8, 2015
Royal Military College of Canada
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Itinerary
Friday, November 6th
1900-2200 Air Liquide Mixer
Tir Nan Og
Saturday, November 7th
0800-0820
Registration and Coffee
0820-0830
Opening Remarks
0830-0930 Plenary Lecture
0930-1000 Coffee Break
1000-1120 Oral Sessions 1-2
1130-1230 Lunch
1230-1330
Poster Set-up/Exhibition
1340-1440
Oral Sessions 3-4
1440-1500
Coffee Break
1500-1620
Oral Sessions 5-6
1630-1830 Poster Session
1900-2355
Banquet
Baronial Hall
Currie Hall
Currie Hall
Massey Hallway
Massey 7 and 15
Cadet Dining Hall
New Gym
Massey 7 and 15
Massey Hallway
Massey 7 and 15
New Gym
Yeo Hall Cadet Mess
Sunday, November 8th
0800-0830 Coffee
1010-1030 Coffee Break
1145-1245
Plenary Lecture 2
1245-1300 Awards and Closing Ceremonies
Massey Hallway
Massey 7 and 15
Massey Hallway
Massey 7 and 15
Currie Hall
Currie Hall
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Bus Schedule: There will be free shuttle buses between the Holiday Inn and the RMCC campus at the
following times:
Saturday between 0730-0800 and 2100-2355
Sunday between 0730-0800 and at 1300
Parking: If you are bringing your own car, there will be free parking in the Sawyer Parking Lot and you will
be issued a parking pass upon coming through the Gate House.
Poster Session: Odd-numbered posters will be judged between 1630-1730; even-numbered posters will be
judged between 1730-1830. Please be at your poster during your appointed time. There will be time to hang
your poster after lunch.
Oral Presentations: Please bring your presentation on a USB stick prior to the start of your session to be
loaded onto the Desktop. Make sure it is PC-compatible.
Exhibition: There will be several companies exhibiting at the conference. Timings to visit the booths are
after lunch between 1230-1330 and during the poster session (1630-1830). The following companies will be
present:
ACS International – CAS
Air Liquide Canada Inc.
Bruker AXS
MEGS Specialty Gases Inc.
Pine Research Instrumentation
Rigaku Oxford Diffraction
Strem Chemicals
Systems for Research
RMC Expo: After lunch, there will be several booths set-up alongside the company booths highlighting
different aspects of RMCC. Please feel free to explore the equipment and ask as many questions as you like!
If the weather is nice, you may also like to go for a walk on the RMCC campus. There will be pamphlets
available outlining the ‘War of 1812 Walking Tour’ around campus. RMCC also has several interesting
military artifacts scattered around the grounds.
Dinner Gala: Please respect the dress code and do not wear jeans.
We would like to give you a brief taste of military Mess Dinner traditions during this year’s IDW Banquet.
At the poster session, there will be a seating plan on display where you will find your name and
corresponding table. There will also be a floor plan to find the location of your table within the Cadet Mess.
Musicians will play at 15 minutes and 5 minutes before the start of dinner.
We kindly ask you to make your way into the Mess starting at 6:30pm and be standing behind your chair at
7:00pm for the arrival of the Head Table.
It is our pleasure to host you at the Royal Military College of Canada Cadet Mess. If you have any questions
or concerns, please do not hesitate to ask any member in uniform.
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5
Air Liquide Mixer
Time:
start at 1900 (Registration ends at 2200)
Where:
Tir Nan Og
200 Ontario St, Kingston, ON K7L 2Y9
(613) 544-7474
https://www.facebook.com/kingston.tirnanog
Musical Entertainment: Tangent
Drink Tickets: black tickets in your badge holder
Tir Nan Og is also open for dinner and offers great pub-style food.
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Gate House
To Kingston
Massey Building – Oral Sessions
(Rooms Massey 7 and 15)
P
Currie Building – Plenary Lectures
(Currie and Baronial Hall)
Yeo Hall – Lunch, Poster Session, Banquet
(Cadet Dining Hall, Mess, and New Gym)
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Program of Events
Saturday, November 7th, 2015
08:00-08:20
Registration and Coffee (Baronial Hall)
08:20-08:30
Opening Remarks: Dr. Gord Simons, Dean of Science, RMCC (Currie Hall)
08:30-09:30
Plenary Lecture: Dr. Ken J. Reimer, Royal Military College of Canada (Currie Hall)
09:30-10:00
Coffee Break (Massey Hallway – Sponsored by New Journal of Chemistry)
10:00-11:20
Oral Session 1
Massey 7
Chair: Anbareen Farooq
10:00
10:20
10:40
Massey 15
Chair: Dr. Michelle Nearing
O1 1,2,4,6-Thiatriazinyl Radicals and Dimers:
Structural and Electronic Tuning through
Heteroaromatic Substituent Modification
O5 New Ruthenium (II) Complex with Pyrazole
Containing Ligand and its Catalytic Activity in
Transfer Hydrogenation
Nathan J. Yutronkie (University of Ottawa), A.A.
Leitch, J.A. Klein, I. Korobkov, J.L. Brusso
Iryna D. Alshakova (Brock University), G.I.
Nikonov
O2 ‘All three-in-one’: Ferromagnetic Interactions,
Single-Molecule Magnetism and Magnetocaloric
Properties in a New Family of [Cu4Ln] Clusters
O6 Synthesis and Biological Activity of FuranContaining Organoruthenium Complexes
Paul Richardson (Brock University), D.I.
Alexandropoulos, L. Cunha-Silva, G. Lorusso, M.
Evangelisti, J. Tang, T.C. Stamatatos
Mohammadmehdi Haghdoost (INRS-Institut), G.
Golbaghi, A. Castonguay
O3 Study of a Novel Hepta-Coordinated FeIII
Bimetalic Complex with an Unusual 1,2,4,5Tetrazine-Ring Opening
O7 Aqueous Biphasic Iron-Catalyzed Asymmetric
Transfer Hydrogenation of Ketones
Maykon A. Lemes (University of Ottawa), A.
Pialat, S.N. Steinmann, I. Korobkov, C. Michel, M.
Murugesu
Karl Z. Demmans (University of Toronto), O.W.K.
Ko, R.H. Morris
O4 A Mononuclear Supramolecular Capsule with
Single Molecule Magnet Behaviour
O8 Catalyst Choice in Cross-Metathesis of
Electron-Deficient Olefins: Phosphine-Induced
Catalyst Decomposition
Majeda Al Hareri (Brock University), E. Gavey,
M. Pilkington
Gwendolyn A. Bailey (University of Ottawa), D.E.
Fogg
11:00
11:30-12:30
Lunch (Cadet Dining Hall)
12:30-13:30
RMCC Exhibition and Poster Set-up (New Gym)
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13:40-14:40
13:40
14:00
Oral Session 2
Massey 7
Chair: Diana Tyner
Massey 15
Chair: Laura Ogilvie
O9 Synthesis and Characterization of Side-Chain
Boron Difluoride Formazanate Polymers
O12 Towards Carrier-Mediated Water Splitting –
Catalytic Dehydrogenation of Formaldehyde
Samantha Novoa (Western University), J.A.
Paquette, S.M. Barbon, R.R. Maar, J.B. Gilroy
Nicholas Alderman (University of Ottawa), C.
Viasus, J. Sommers, V. Peneau, L. Hull, S. Alshehri,
S. Gambarotta
O10 Alkyl-Functionalization of 3,5-Bis-(2-Pyridyl)1,2,4,6-Thiatriazine Complexes
O13 Catalytic Hydrogenation of CO2 to Formamide
using Non-precious Metal Catalysts
Elizabeth Kleisath (University of Ottawa), N.
Yutronkie, I. Korobkov, B. Gabidullin, J. Brusso
Mohammad A. Affan (Queen’s University), P.G.
Jessop
O11 Towards Highly Conjugated and Functional
Materials: the Quest for Polyazaborinines
O14 Ruthenium and Iridium Complexes of PolyPyridine Ligands as Homogeneous Catalysts for the
Hydrodeoxygenation of Biomass-Derived Substrates
to Value-Added Chemicals
Soren Mellerup (Queen’s University), S. Wang
Elnaz Latifi (University of Guelph), R.J. Sullivan,
T.A. Minard, C.T. Oswin, M. Schlaf
14:20
14:40-15:00
Coffee Break (Massey Hallway – Sponsored by Systems for Research)
15:00-16:20
Oral Session 3
15:00
15:20
Massey 7
Chair: Summer Li
Massey 15
Chair: Jessica Henry
O15 A Fluorescent Radical-Functionalized PolyAromatic Hydrocarbon Polymer Composite
O19 Synthesis and Coordination of Amidines and
Phosphaamidines Metal Complexes
Mitchell Nascimento (University of Windsor), Y.
Beldjoudi, I. Osorio-Roman, J.M. Rawson
Ramjee Kandel (Queen’s University), K. Huynh, L.
Dalgliesh, R. Wang, P.G. Jessop
O16 Multichromic Supramolecular Dye
Architectures for Advanced Light-Harvesting
Applications
O20 Manganese(II) Dialkyl and Manganese(I) and
(III) Hydride Complexes
Muhammad Yousaf (Ryerson University), B.D.
Koivisto
Jeffrey S. Price (McMaster University), P. Chadha,
D.J.H. Emslie
O17 The Formation of Gold Thiophene Nanoreactor
By Mediating Metal-Polymer Interaction
O21 Nitrene Transfer from Organic Azides
Mediated by Metal Complexes of Bulky oPhenylenediamide Ligand
Vishva Shah (Royal Military College of Canada),
C. Malardier-Jugroot, M. Jugroot
Pavel Zatsepin (University of Toronto), T. Janes, D.
Song
O18 Electrochemical Characterizations of UltraStable Self-assembled Monolayers of NHeterocyclic Carbenes on Gold
O22 Solvent Stabilized Dinitrogen Trioxide as a
Laboratory Reagent
Zhe She (University of Toronto Scarborough), M.R.
Narouz, C.A. Smith, C.M. Crudden, J.H. Horton, H.B. Kraatz
Kristopher Rosadiuk (McGill University), D.S.
Bohle
15:40
16:00
16:30-18:30
Poster Session and Exhibition (New Gym) (red drink tickets in your badge holders)
19:00
Banquet (Yeo Hall)
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Sunday, November 8th, 2015
08:00-08:30
Registration and Coffee (Baronial Hall)
08:30-10:10
Oral Session 4
08:30
08:50
09:10
09:30
Massey 7
Chair: Vishva Shah
Massey 15
Chair: Matt McTaggart
O23 Evaluation of Anisole-Substituted Boron
Difluoride Formazanate Complexes for
Fluorescence Cell Imaging
O28 Iterative, Protecting Group Free SuzukiMiyaura Coupling of Enantioenriched
Polyboronates
Ryan R. Maar (Western University), S.M. Barbon,
N. Sharma, H. Groom, L.G. Luyt, J.B. Gilroy
C. Ziebenhaus, Jason Rygus (Queen’s University),
K. Ghozati, P.J. Unsworth, S. Voth, Y. Maekawa,
C.M. Crudden, M. Nambo
O24 Pyrido[2,1-a]-isoindole as a Novel Ligand in
Main Group and Transition Metal Chemistry
O29 Chan-Lam Coupling Using a Copper(II)
Complex with a Sulfonated Diketimine Ligand
Sean M. McDonald (Queen’s University), S. Wang
Valérie Hardouin Duparc (Université de
Montréal), F. Schaper
O25 Bis-Carbene-Stabilized Phosphorus Cations
O30 Stable Organopalladium(IV) Aryldiazenido
Complexes
Justin F. Binder (University of Windsor), A.
Swidan, M. Tang, J.H. Nguyen, C.L.B. Macdonald
David Armstrong (University of Toronto
Mississauga), M. Daryanavard, A.J. Lough, U.W.
Fekl
O26 Engineered Designer Monomers: The Path to
Light and Moisture Stable Polystannanes
O31 Selective C(sp2)-O Bond Formation from
Palladium Complexes by Using a Green Oxidant
Jeffrey Pau (Ryerson University), D. Foucher
Ava Behnia (Western University), J.M. Blacquiere,
R.J. Puddephatt
O27 N-Heterocyclic Carbene Stabilized Ag
Nanoparticles
O32 Tuning the Steric and Electronic Properties of
Iron-Based Catalysts Using Modular Phosphine
Moieties
Iraklii I. Ebralidze (University of Toronto
Scarborough), H.-B. Kraatz
Samantha A. M. Smith (University of Toronto),
A.J. Lough, R.H. Morris
09:50
10:10-10:30
Coffee Break (Massey Hallway)
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10:30-11:30
10:30
10:50
11:10
Oral Session 5
Massey 7
Chair: Shuang Liang
Massey 15
Chair: Dr. Deborah Durbin
O33 Intercalation of Coordinatively Unsaturated
FeIII Ion within Interpenetrated MOF-5
O36 Ligand Effects in Copper-Catalyzed Aerobic
Oxygenation of Phenols
Rebecca J. Holmberg (University of Ottawa), T.
Burns, S.M. Greer, L. Kobera, S.A. Stoian, I.
Korobkov, S. Hill, D.L. Bryce, T.K. Woo, M.
Murugesu
Laura Andrea Rodríguez Solano (Concordia
University), J.-P. Lumb, X. Ottenwaelder
O34 Towards Modeling the Active Site of
Photosystem II: New Structural Motifs in Mn/Ca
Chemistry from the Use of Salicylhydroxime
O37 1,2-Diphosphonium Dication : A Strong PBased Lewis Acid in Frustrated Lewis Pair
Activations of B-H, Si-H, C-H and H-H Bonds
Alysha A. Alaimo (Brock University), S.J. Teat, G.
Christou, T.C. Stamatatos
Julia M. Bayne (University of Toronto), M.H.
Holthausen, I. Mallov, R. Dobrovetsky, D.W.
Stephan
O35 Single Molecule Magnets (SMM)
O38 Progress in Boro-cation Catalysis for
Hydrofunctionalization
Munendra Yadav (McGill University), S. Bohle
Patrick Eisenberger (Queen’s University), C.M.
Crudden
11:45-12:45
Plenary Lecture: Dr. Daniel J. Mindiola, University of Pennsylvania (Currie Hall)
12:45-13:00
Closing Ceremonies and Awards (Currie Hall)
11
Plenary Speaker - Dr. Ken J. Reimer
Emeritus Professor
Department of Chemistry and Chemical Engineering, Royal Military College of Canada
Ken Reimer received his BSc (1969) and MSc (1971) degrees from the University
of Calgary; the latter dealing with tungsten and molybdenum complexes and his
PhD (1975) from the University of Western Ontario in organometallic synthesis. He
then studied bioinorganic chemistry as a Killam Postdoctoral Fellow at the
University of British Columbia. After teaching briefly at the University of Guelph,
he was appointed as an Assistant Professor at Royal Roads Military College in
Victoria, BC, reaching the rank of Professor before being transferred to the Royal
Military College of Canada in 1995. He also holds a cross-appointment to Queen’s
University School of Environmental Studies. Upon his retirement from RMCC in
2014, Dr. Reimer was appointed Emeritus Professor and he still maintains an active
research program.
Starting with a background in classical inorganic chemistry, Ken became very interested in interdisciplinary
research. This led to a focus on arsenic in the environment and included numerous sampling programs in the
coastal waters of BC to examine the effect of mine waste disposal. Environmental risk assessment was just
beginning and found application interpreting the results of these investigations that had an applied and public
component. Ken’s group expanded to include biologists and oceanographers as well as chemists and he
extended his collaboration with researchers in several other disciplines. In 1989, Dr. Reimer founded, and for
the next 25 years was Director of, the Environmental Sciences Group (ESG), a multidisciplinary team (of 60100 people) that conducted basic and applied environmental research all over the world. ESG was the
scientific authority for the Distant Early Warning Line cleanup – one of Canada’s largest remediation
projects. It involved some of the first environmental site assessments in Canada’s Arctic; the design of the
cleanup protocol; numerous consultations with Inuit; and oversight of the actual remediation itself. This is
just one of the hundreds of projects that typically involved remote locations, novel applications of human
health and ecological risk assessment, actual environmental cleanups and extensive interactions with
aboriginal communities. Arsenic continued to be a basic research focus but the applied work brought interest
in a diverse range of contaminants including persistent organic pollutants, chromium, lead, and cadmium.
Dr. Reimer’s creation of the ESG and its successful involvement with environmental restoration was
rewarded with two National Defence Deputy Minister Commendation Awards in 1992 and 2006. He has also
received the Chemical Institute of Canada’s Environmental Improvement Award and the RMCC Cowan
Prize for Excellence in Research. Ken has always been committed to making the results of his work
meaningful to stakeholders and, for that reason, he is particularly proud of a Real Property Institute of
Canada Award of Excellence in the Field of Contaminated Sites entitled ‘Scientists and Inuit - A Long Term
Partnership’ and a Parks Canada CEO Award of Excellence ‘for an extraordinary contribution in engaging
partnerships with the Inuvialuit. Ken is a Past Chair of the Environment Division of the Chemical Institute of
Canada and is the current Chair of BioAcessibility Research Canada.
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Plenary Speaker - Dr. Daniel J. Mindiola
Presidential Professor
Department of Chemistry, University of Pennsylvania
Daniel José Mindiola was born in San Cristóbal, Venezuela in 1974. Upon entering
the US with his mother in 1989, Daniel then pursued the remainder of high school in
a small town in mid-Michigan (Ovid). Daniel began his college education at
Michigan State University, East Lansing, MI, in 1992. As a "Spartan", he spent the
next three and a half years learning the principles of inorganic chemistry under the
auspices of Professor Kim R. Dunbar. After obtaining his B.S. degree in chemistry
from MSU in 1996, Daniel then attended the Massachusetts Institute of Technology
in Cambridge, MA, under the guidance of Professor Christopher "Kit" Cummins. In
the summer of 2000, Daniel completed his PhD. degree and continued work in small
molecule chemistry as an NIH and FORD post-doctoral fellow in the laboratories of
Professor Gregory L. Hillhouse at the University of Chicago.
After nearly two years at Chicago, Daniel accepted an invitation to join the Chemistry Faculty at Indiana
University in the city of Bloomington, IN (July of 2002). In 2007, he was promoted to Associate Professor
with tenure, and in 2011 to Full Professor. He was the departmental Graduate Advisor from 2008-09 and
Chair of Graduate Admissions at IU-Chemistry from 2010-2013. His research work entails the design and
assembly of reactive metal complexes of early metals (in particular 3d metals) and their role in unusual
transformations such as C-H activation and C-N bond cleavage reactions. He is also interested in novel
catalytic processes mediated by reactive complexes containing metal-ligand multiple bonds.
In the summer of 2013 and after 11 wonderful years in Bloomington, Daniel moved to the University of
Pennsylvania where he holds a Presidential Chair Professorship. In 2014, Daniel was elected as a Fellow of
the Royal Society of Chemistry (FRSC) and is Associate Editor for the ACS journal Organometallics. He
formally was an Associate Editor for Dalton Transactions for 3 years. He has given over 140 lectures
worldwide and published over 140 papers in peer-reviewed journals. Other accolades prior to 2013 include:
Fellow, Japan Society for the Promotion of Science; Fellow, Chemistry Research Promotion Center, National
Science Council of Taiwan; College of Natural Science Recent Alumni Award (Michigan State University);
American Chemical Society National Fresenius Award (Phi Lambda Upsilon); Friedrich Wilhelm Bessel
Research Award (Humboldt Foundation); Dalton Lecture Award; University of California at Berkeley;
Camille and Henry Dreyfus New Faculty Award; NSF Presidential Early Career Award for Scientists and
Engineers (PECASE); Alfred P. Sloan Research Fellow; Camille Dreyfus Teacher-Scholar Award; and NSF
CAREER Award.
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Plenary Lecture 1 – Saturday, November 7th, at 08:30 in Currie Hall
Arsenic in the environment, in consumer products, and in you.
Are you at risk?
Ken J. Reimer
Environmental Sciences Group, Department of Chemistry and Chemical Engineering, Royal
Military College of Canada
Email: reimer-k@rmc.ca
Recent media articles shock readers with statements like: ‘Arsenic in rice and baby foods’, ‘Arsenic in Red
Wine’, and ‘Arsenic in Apple Juice’ (with the quote: ‘I didn’t know that I was giving poison to my child’).
These attract attention because most people feel that arsenic is synonymous with poison. Arsenic (as arsenic
trioxide) is poisonous and in the Middle Ages was readily available from smelting of gold ore. It was also
colourless, odourless, and tasteless and became so popular that it was known as the ‘King of Poisons’.
Popular writers like Agatha Christie and plays like ‘Arsenic and Old Lace’ further popularized the notion that
arsenic had to be bad.
The real situation is somewhat more complex. For example, when I am asked to comment on those
newspaper headlines I respond with a statement that is counterintuitive to many people. I say ‘of course we
should find arsenic in rice; arsenic is everywhere and it would be more surprising if we did not find it in our
food and drink.’
This talk will describe the ubiquitous presence of arsenic in our environment. Arsenic is present in over 300
minerals and natural weathering processes, together with biogeochemical transformations, redistribute
arsenic into approximately 50 different chemical forms. We know how most of these transformations take
place, including how humans metabolize arsenic, but the production of the one non-toxic arsenical –
arsenobetaine, continues to elude us. We also know that high doses of inorganic arsenic will cause numerous
health effects, including cancer, but there is an intense debate about possible health effects caused by the low
dose that we all experience each day. Low dose may be the norm, but there are situations (such as old mine
sites) where arsenic has been redistributed in the environment in very large amounts. Case studies will be
used to examine how chemists can assist in dealing with such problems and with public concerns regarding
arsenophobia.
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Plenary Lecture 2 – Sunday, November 8th, at 11:45 in Currie Hall
New Developments in Dehydrogenation of Volatile Alkanes with Ti-C Multiple
Bonds.
Daniel J. Mindiola
Department of Chemistry, University of Pennsylvania, Philadelphia, PA
E-mail: mindiola@sas.upenn.edu
We will present the reactivity of a transient titanium alkylidyne (PNP)Ti≡CtBu (PNP = N[2-P(CHMe2)2-4methylphenyl]2–), specifically how this species engages in intermolecular C-H activation and
functionalization reactions. Such species can dehydrogenate methane, and C2-C8 alkanes selectively at the
terminal position (in the case of linear alkane C4-C8) to form the olefin product. The mechanism to this
transformation as well as other new reactions such as the dehydrogenation of cyclohexane and trapping
reactions will be presented and discussed. A new catalytic cycle for dehydrogenation of alkanes will be also
discussed as well as the formation of new Ti-C mulitiply-bonded scaffolds such as phosphino-alkylidenes
and alkylidynes and phosphonio-alkylidynes.
15
O1
1,2,4,6-Thiatriazinyl Radicals and Dimers: Structural and Electronic Tuning
through Heteroaromatic Substituent Modification
Nathan J. Yutronkie, Alicea A. Leitch, Jacob A. Klein, Ilia Korobkov, and Jaclyn L. Brusso *
Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, Ottawa,
ON, Canada
nyutr055@uottawa.ca; jbrusso@uottawa,ca
For some time, thiazyl-based neutral radicals have been recognized as attractive candidates for molecular conductors
and magnets, in addition to implementation as spin-bearing ligands or liquid
crystalline radicals. The 1,2,4,6-thiatriazinyl (TTA) radical is an ideal system in
regards to the aforementioned applications as variation in the R substituent can
be used to alter the molecular and solid state properties. To this end, a series of
TTA radicals have been prepared and investigated with substituted
heteroaromatic susbstituents (e.g. thienyl, pyridyl, pyrimidyl). The 3,5-bis(2pyridyl)-1,2,4,6-thiatriazinyl (Py2TTA) and 3,5-bis(2-pyrimidyl)-1,2,4,6thiatriazinyl (Pm2TTA) radicals can been viewed as attractive candidates
towards spin-bearing ligands with binding motifs sturcturally similar to
terpyridine. Additionally, the 3,5-bis-(2-thienyl)-1,2,4,6-thiatriazinyl radical (Th2TTA) has been targeted as building
blocks in multifuctional materials as facile functionalization on the thienyl substutuents can give rise to the potential of
discotic liquid crystalline materials. This presentation will focus on the development of these radicals in regards to their
synthesis, characterization, and crystal structures.
O2
‘All Three-in-One’: Ferromagnetic Interactions, Single-Molecule Magnetism and
Magnetocaloric Properties in a New Family of [Cu4Ln] Clusters
Paul Richardson,1 Dimitris I. Alexandropoulos,1 Luís Cunha-Silva,3 Giulia Lorusso,4 Marco Evangelisti,4 Jinkui
Tang,2 and Theocharis C. Stamatatos*,1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; State Key Laboratory of Rare
Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
3
Changchun, P. R. China; REQUIMTE / LAQV & Department of Chemistry and Biochemistry, Faculty of
4
Sciences, University of Porto, Porto, Portugal; Instituto de Ciencia de Materiales de Aragón (ICMA) and
Departamento de Física de la Materia Condensada, CSIC-Universidad de Zaragoza, Zaragoza, Spain
pr07xq@brocku.ca; tstamatatos@brocku.ca
Modern coordination chemistry, as a field of scientific research, has expanded greatly over the past decades, finding
interests in not only isolating aesthetically pleasing structures, but also probing the magnetic properties of these
compounds, such as single-molecule magnetism (SMM) or the magnetocaloric effect (MCE). These two phenomena
share common characteristics; both are enhanced by a high-spin ground state,
which mainly arises from ferromagnetic interactions between the metal ions
present. The desire for high-spin molecules, which is aided by a large number of
unpaired electrons in the metal ion(s), lead to the employment of lanthanide (Ln)
ions, either in homometallic 4f- or heterometallic 3d/4f-chemistry. To form such
high-spin molecules, the use of different ligands must be investigated; both
bridging and chelating ligands are necessary to increase the nuclearity and
thermodynamic stability of the compound and simultaneously prevent the
extensive polymerization of the metal ions. Through the use of the bridging and
chelating ligand naphthalene-2,3-diol (ndH2), a new [Cu4Ln] family of clusters
was isolated and characterized (Figure). This family was studied in detail with
respect to their magnetic properties, searching for SMM behaviour in both the
TbIII and DyIII analogues, as well as MCE in the Gd III analogue.1
5Figure. Structure of [Cu4Gd(nd)8]
1.
P. Richardson, D. I. Alexandropoulos, L. Cunha-Silva, G. Lorusso, M.
Evangelisti, J. Tang, Th. C. Stamatatos, Inorg. Chem. Front. 2015, 2, 945.
16
O3
Study of a Novel Hepta-coordinated FeIII Bimetalic Complex with an Unusual
1,2,4,5-Tetrazine-Ring Opening
Maykon A. Lemes,a Amélie Pialat,a Stephan N. Steinmann,b Ilia Korobkov,a Carine Michel,b and Muralee
Murugesua,*
a
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada;
Laboratoire de Chimie UMR5182, Université de Lyon, CNRS, Ecole Normale Supérieure de Lyon, Lyon
cedex 07, France
mleme031@uottawa.ca; m.murugesu@uottawa.ca
b
Reaction of Fe(NO3)3 with 3,6-di(pyrimidin-2-yl)-1,2,4,5-tetrazine (BPymTz) in acetonitrile gives a hepta-coordinated
FeIII complex (1) with the bridging unit 1,2-diiminohydrazido (1,2-dih2- : —HN—C(R)=N—N=C(R)—NH—) generated
in-situ from the tetrazine ring-opening of BPymTz. DFT calculations, X-ray diffraction studies and SQUID
magnetometry measurements, have been performed on 1. The crystallography measurement confirms the ring-opening
and the substituent’s contribution to the rare pentagonal bipyramidal coordination geometry of the metal ions. Magnetic
susceptibility measurements performed on 1 reveal an S = 0 ground state, arising from a weak antiferromagnetic
interaction between the two FeIII centres (J = -3.025 cm-1).
O4
A Mononuclear Supramolecular Capsule with Single Molecule Magnet Behaviour
Majeda Al Hareri, Emma Gavey, and Melanie Pilkington*
Department of Chemistry, Brock University, St. Catharines, ON, Canada
ma10hk@brocku.ca; mpilkington@brocku.ca
Many lanthanide ions display great potential in the field of molecular magnetism due
to their high intrinsic anisotropies1, which can be enhanced by an appropriate
coordination environment. However, many of the ligand systems employed to date
require multi-step syntheses and result in complexes which are unstable to air or
moisture.1,2 Our approach has been to make use of the inherently oxophilic nature of
lanthanide ions and employ oxygen-rich ligands, such as the tuneable crown ethers.
Our group has recently reported the synthesis of a novel family of half-sandwich and
sandwich-like complexes that exhibit single molecule magnet (SMM) behaviour.3 A
new addition to this family, a mononuclear DyIII capsule (1) comprising of three Hbonded benzo-15-crown-5 ligands, also exhibits the slow relaxation of magnetization
consistent with SMM properties. This family collectively represents the first example
of the exploitation of crown ethers as ligands for the formation of mononuclear lanthanide SMMs.
1
D. N. Woodruff, R.E.P. Winpenny, R.A. Layfield, Chemical Reviews, 2013, 113, 7, 5110-5148.; 2 F. Chibotaru, M.
Murugesu et al., Journal of the American Chemical Society, 2013, 135, 3502-3510.; 3 M. Pilkington et al., J. Mater.
Chem. C, 2015, 3, 7738.
17
O5
New Ruthenium (II) Complex with Pyrazole Containing Ligand and its Catalytic
Activity in Transfer Hydrogenation
Iryna D. Alshakova and Georgii I. Nikonov*
iryna.alshakova@brocku.ca; gnikonov@brocku.ca
Ruthenium occupies a prominent position in catalytic hydrogenation and transfer hydrogenation (TH) of unsaturated
substrates. Several families of bifunctional Ru-based catalysts have been developed. Recently, heterocycle-based
ligands have received significant attention, and in particular pyrazole-supported Ru complexes were found to be
effective in the catalytic TH.[1] Given these literature precedents and our previous research on phosphine supported
catalytic TH of challenging substrates, we designed of a new bifunctional pyrazole-phosphine ligand (N,P). Screening of
potential Ru catalysts resulted in the preparation of complex 1 which happened to be a highly active catalyst for the TH
of nitriles, olefins, and heteroaromatics.
1
[1] a) S. F. L. T. Ghoochany, Y. Sun, and W.R. Thiel, Eur. J Inorg. Chem. 2011, 3431-3437; b) P. W. W. Du, Q.
Wang, and Z. Yu, Organometallics 2013, 32, 3083-3090.
O6
Synthesis and Biological Activity of Furan-Containing Organoruthenium
Complexes
Mohammadmehdi Haghdoost, Golara Golbaghi, and Annie Castonguay*
INRS-Institut Armand-Frappier, Laval, QC, Canada
Mehdi.Haghdoost@iaf.inrs.ca; Annie.Castonguay@iaf.inrs.ca
Transition metal complexes have unique properties, notably due to their partially filled d-orbitals, and can offer great
opportunities to the field of chemotherapy, leading to the discovery of new modes of action for therapeutics and novel
interactions with biomolecules. Of particular interest, ruthenium complexes display great advantages over platinumbased drugs that are commonly used for cancer therapy. Our research aims at the discovery of novel multitasking
anticancer drug candidates, by combining ruthenium complexes and biologically active organic molecules.
Numerous furan-containing compounds were reported to display anticancer, as well as anti-inflammatory and
antimicrobial activities. As an added value, the presence of a furan ring in the backbone of inorganic complexes offers
the unique possibility to link them to cancer cell targeting agents or drug delivery systems via furan-maleimide DielsAlder cycloadditions. This type of linkage can then undergo thermal disassembly at physiological temperature, and
allow the release of furan-containing therapeutics.
The focus of this presentation will be on the synthesis and characterization of Ru(II)-arene complexes with pendant
furan arms, and our preliminary results regarding their in vitro anticancer activity against human breast cancer cells.
18
O7
Aqueous Biphasic Iron-Catalyzed Asymmetric Transfer Hydrogenation of Ketones
Karl Z. Demmans, Oliver W. K. Ko,* and Robert H. Morris*
Department of Chemistry, University of Toronto, Toronto, ON, Canada
kdemmans@chem.utoronto.ca; oliver.ko@mail.utoronto.ca; robert.morris@utoronto.ca
For the first time, an iron (II) catalyst is used in the biphasic asymmetric transfer hydrogenation (ATH) of ketones to
enantioenriched alcohols employing water and potassium formate as the proton and hydride source. The precatalyst
[FeCl(CO)(P-NH-N-P)][BF4] (P-NH-N-P = (S,S)-PPh2CH2CH2NHCHPhCHPhNCHCH2PPh2) in the organic phase with
the substrate is activated by base to produce a system that rivals the best ruthenium biphasic ATH catalysts in activity
but not enantioselectivity. Biorenewable 2-methyltetrahydrofuran was added as a cosolvent to greatly enhance the
catalyst’s activity. The enantioselectivity of the reduction ranged from 3 to 88% depending on the substitution pattern of
the
arylketone
employed.
NMR
studies
verify
the
formation
of
an
iron
hydride
[FeH(CO)(PPh2CH2CH2NHCHPhCHPhNCHCHPPh2] intermediate as was observed in our 2-propanol-based ATH
studies.
O8
Catalyst Choice in Cross-Metathesis of Electron-Deficient Olefins: PhosphineInduced Catalyst Decomposition
Gwendolyn A. Bailey and Deryn E. Fogg*
Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, ON, Canada
gbail025@uottawa.ca; dfogg@uottawa.ca
In the past two years, olefin metathesis has seen its longawaited implementation in pharmaceutical and specialtychemicals manufacturing.1,2 Fundamental questions relating to
catalyst deactivation pathways hence take on intensified
importance. We recently described the incompatibility of the
dominant Grubbs catalyst GII (Chart 1) with acrylates. The
PCy3 ligand used to stabilize the precatalyst reacts with these
electron-deficient olefins to generate strongly basic enolate A,
which then triggers catalyst decomposition by abstracting a proton from the metallacyclobutane intermediate.3 The
scope of this behaviour is of keen interest from the emerging perspective of metathesis of directly-functionalized
olefins. Here we explore its dependence on the electronic nature of the olefin substituent, and on the basicity of the
phosphine ligand.
[1] (a) Nickel, A.; Pederson, P. L. in Olefin Metathesis – Theory and Practice (Ed.: K. Grela), Wiley, Hoboken, 2014,
pp. 335–348. (b) Fandrick, K. R.; Savoie, J.; Yee, N; Song, J. J.; Senanayake, C. H. in Olefin Metathesis – Theory and
Practice (Ed.: K. Grela), Wiley, Hoboken, 2014, pp. 349–366.
[2] Higman, C. S.; Lummiss, J. A. M.; Fogg, D. E. Angew. Chem. Int. Ed. 2016, accepted.
[3] Bailey, G. A.; Fogg, D. E. J. Am. Chem. Soc. 2015, 137, 7318–7321.
19
O9
Synthesis and Characterization of Side-Chain Boron Difluoride Formazanate
Polymers
Samantha Novoa, Joseph A. Paquette, Stephanie M. Barbon, Ryan R. Maar, and Joe B. Gilroy*
Department of Chemistry, Western University, London, ON, Canada
snovoa@uwo.ca; joe.gilroy@uwo.ca
Boron difluoride (BF2) complexes of formazanate ligands (e.g., 1) are
a class of molecular materials that offer structurally tunable
spectroscopic properties, moderate to high fluorescence quantum
yields and redox activity.1 Due to their promising properties, we set
out to incorporate triaryl formazanate BF2 complex 1 into polymers 2
through ring-opening metathesis polymerization (ROMP) of a pendant
norbornene group using Grubbs' 3rd generation catalyst (GIII). 2
Mechanistic studies revealed the controlled nature of this
polymerization. Moreover, the unique properties of the BF 2 complex
were retained upon polymerization. The polymers are strongly
absorbing in the visible region, are fluorescent, exhibit large Stoke's
shifts, and can be reversibly reduced to borataverdazyl-based poly(radical anions) electrochemically. Recent progress in
this area will be presented.
1. S. M. Barbon, P. A. Reinkeluers, J. T. Price, V. N. Staroverov and J. B. Gilroy, Chem. Eur. J., 2014, 20,
1134011344.
2. S. Novoa, J. A. Paquette, S. M. Barbon, R. R. Maar, J.B. Gilroy, 2015, Submitted.
O10
Alkyl-functionalization of 3,5-bis-(2-pyridyl)-1,2,4,6-thiatriazine Complexes
Elizabeth Kleisath, Nathan Yutronkie, Ilia Korobkov, Bulat Gabidullin, and Jaclyn Brusso *
Department of Chemistry, University of Ottawa, Ottawa, ON, Canada
eklei031@uottawa.ca; jbrusso@uottawa.ca
A novel synthesis of alkyl-functionalized 3,5-bis(2-pyridyl)-4-hydro-1,2,4,6-thiatriazine (Py2TTAH) complexes through
post thiatriazine (TTA) ring formation will be presented. This marks the first reported example of S-alkylation in TTA
complexes starting from a stable synthetic precursor. Either discrete cations or coordination polymer structures are
obtained, depending on the electrophilicity of the
alkylating agent used. In addition, the relative
susceptibility of the Py2TTAH heteroatoms
towards alkylation was determined; initial
alkylation occurred at the sulfur of the TTA ring,
and then additionally on the nitrogen atoms of
the pyridine substituents. Single crystal X-ray
analysis highlights the differences in chemical
environment and crystallographic packing
between the discrete molecules in comparison to
the 1D coordination polymer. The versatile
heteroatom-alkylation synthesis for TTAs will be
presented, along with characterization studies of
the resulting compounds.
20
O11
Towards Highly Conjugated and Functional Materials: the Quest for
Polyazaborinines
Soren Mellerup and Suning Wang*
Department of Chemistry, Queen’s University, Kingston, ON, Canada
soren.mellerup@chem.queensu.ca; suning.wang@chem.queensu.ca
Recently, our research group observed that BN-heterocycles (B; Figure 1) display unique reactivity when exposed to
different stimuli such as heat or light, ultimately generating either pyrido[1,2-a]isoindole (A) or BN-phenanthrenes (C)
respectively.1 Due to the simplicity and selectivity of each transformation, we set out to design new precursors
consisting of multiple BN-heterocyclic components such that the application of either heat or light would induce the
formation of highly -conjugated materials
containing several pyrido[1,2-a]isoindole or
BN-phenanthrene
functionalities.
This
presentation will focus on the synthesis of
these
interesting
molecules,
their
photo/thermal reactivities, and evaluation of
the highly conjugated products.
Figure 1. The varying reactivity of BN-heterocyles B.
1) Yang, D.T.; Mellerup, S.K.; Wang, X.; Lu, J.S.; Wang, S. Angew. Chem. Int. Ed. 2015, Accepted.
O12
Towards Carrier-Mediated Water Splitting – Catalytic Dehydrogenation of
Formaldehyde
Nicholas Alderman, Camilo Viasus, Jacob Sommers, Virginie Peneau, Laura Hull, Salimah Alshehri, and Sandro
Gambarotta*
nickalderman@gmail.com; sgambaro@uottawa.ca
A major problem with current photochemical water splitting systems such as TiO 2 is the inhibitive cost of gas (O2/H2)
separation, which can add hundreds of million dollars to plant designs. Therefore a system which can release carbon and
hydrogen in two different environments would negate the need for expensive gas separation. We propose a catalytic
cycle based upon the oxidation and reduction of a carbon carrier, expelling hydrogen in one step and re-hydrogenation
(using water and releasing oxygen) in another step. We have been investigating the use of the formaldehyde-formate
couple, and show promising preliminary results in an overall water splitting cycle using this technique.
21
O13
Catalytic Hydrogenation of CO2 to Formamide using Non-precious Metal Catalysts
Mohammad A. Affan and Philip G. Jessop*
12maa7@queensu.ca; jessop@queensu.ca
Catalytic hydrogenation of CO2 is an efficient and selective way to form value added fine chemicals such as formic acid
derivatives, but most of the highly active catalysts have required precious metals. Eighteen non-precious metal
precursors have been screened with six types of phosphine/hemilabile ligands for the catalytic hydrogenation of CO 2
with morpholine to formamide. Twelve non-precious metal precursors have also been screened with two diphosphine
ligands for the catalytic hydrogenation of CO2 with 2-ethylhexylamine to formamide. The most active catalysts for the
hydrogenation of CO2 for the formylation of morpholine or 2-ethylhexylamine are [MX2(dmpe)2] (M = Fe(II) and
Ni(II); X = Cl-, CH3CO2-; acac-; dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO. Morpholine and 2ethylhexylamine are formylated at 100 oC and 135 oC, respectively, at a total pressure of 100 bar. Morpholine was
formylated with a TON up to 18,000, which is approaching the range of TON values reported for noble metal-phosphine
complexes. 2-Ethylhexylformamide was obtained with a TON up to 1,600. With the appropriate selection of catalyst
and reaction conditions, >90-98% conversion of amine was achieved to form a formamide.
O14
Ruthenium and Iridium Complexes of Poly-pyridine Ligands as Homogeneous
Catalysts for the Hydrodeoxygenation of Biomass-derived Substrates to Valueadded Chemicals
Elnaz Latifi, Ryan J. Sullivan, Thomas A. Minard, Christopher T. Oswin, and Marcel Schlaf *
Department of Chemistry, University of Guelph, Guelph, ON, Canada
elatifi@uoguelph.ca; mschlaf@uoguelph.ca
The series of the water-soluble tri/tetradentate amino-poly-pyridine ligand based homogeneous Ruthenium/Iridium
catalysts (1-5) was evaluated for the conversion of biomass derived 2,5-hexanedione and 2,5-dimethylfuran to the
hydrodeoxygenated value-added products 2,5-hexanediol, 2,5-dimethyltetrahydrofuran and hexane in aqueous acidic
medium at high temperatures (150−225 °C) under hydrogen gas (5.5 MPa). The systems are active but limited by
thermal decomposition. Catalyst (1) decomposes at T ≥ 225 °C to the inactive bis-chelate complex [(4′-Ph-terpy)2Ru]2+
and an inactive metallic ruthenium coating. 2 decomposes at T > 175 °C acting as a heterogeneous Ir0 catalyst. 3
decomposes at T ≥ 175 °C by formation of marginally active Ru0. 4 also shows good activity for the conversion of 2,5hexanedione to 2,5-hexanediol and 2,5-dimethyltetrahydrofuran at 175 and 200 °C with decomposition observed only at
T ≥ 225 °C. 5 is capable of converting 5-hydroxy-methylfurfural-acetone aldol adducts to the highly valuable 2,5,8nonatriol in moderate yields, but deactivation via formation of the bis-chelate was again observed at T ≥ 200 °C.
22
O15
A Fluorescent Radical-Functionalized Poly-Aromatic Hydrocarbon Polymer
Composite
Mitchell Nascimento, Yassine Beldjoudi, Igor Osorio-Roman, and Jeremy M. Rawson*
Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, Canada
nascime@uwindsor.ca; jmrawson@uwindsor.ca
Radicals have recently been proposed as excellent candidates for light-emitting devices such as OLEDs due to their
theoretical 100% efficient doublet excitation/relaxation process1. Here we describe a phenanthrene-functionalised
dithiadiazolyl radical (1). The radical is a diamagnetic dimer in the solid state but dissociates to form monomers in
solution. Spectroscopic studies reveal excitation at 254 nm affords a bright blue
emission at 410 nm. TD-DFT studies indicate that the initial absorption giving rise to
the fluorescence is not radical based and the non-participation of the radical electron in
the fluorescence process is evidenced by the observation that the salt [1][GaCl4]
exhibits a similar broad emission at 410 nm. Incorporation of 1 into PMMA and PS
polymer matrices afford smooth homogeneous blue emissive polymer films whose
lifetimes are 10 to 100 times greater than 1 in solution.
1. Q. Peng, A. Obolda, M. Zhang and F. Li, Angew. Chem. Int. Ed., 2015, 54, 7091.
O16
Multichromic Supramolecular Dye Architectures for Advanced Light-Harvesting
Applications
Muhammad Yousaf and Bryan D. Koivisto*
Department of Chemistry and Biology, Ryerson University, Toronto, ON, Canada
myousaf@ryerson.ca; bryan.koivisto@ryerson.ca
Shape-persistent phenylacetylene macrocycles have been explored in a number of optoelectronic and light-harvesting
applications, including two-photon absorption. Likewise, BODIPY
(4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes) dyes have also been
extensively used in material applications, owing to their tunable,
intense absorption and sharp emission peaks exhibiting high quantum
yields. Employing the BODIPY molecule orthogonal to the
phenylacetylene-macrocycle results in energy transfer from macrocycle
to the BODIPY core. The novel dye design could potentially be used in
the dye-sensitized solar cells (DSSCs). The DSSC is a next-generation
photovoltaic device that incorporates a dye molecule as a lightabsorber. The dyes for the DSSC are generally comprised of a redoxactive donor/chromophore (D) that is coupled through a conjugated
linker (π) to an acceptor (A) capable of anchoring to TiO2 (i.e. D-π-A
motif). The BODIPY-macrocycle dye motif can be used as a π-spacer
in the DSSC dye (as shown in Fig.) and could permit two-photon
absorption resulting in panchromatic absorption.
23
O17
The Formation of Gold Thiophene Nanoreactor by Mediating Metal-Polymer
Interaction
Vishva Shah,1 Cecile Malardier-Jugroot,1,* and Manish Jugroot2
1
2
Department of Chemistry and Chemical Engineering; Department of Mechanical and Aerospace
Engineering, Royal Military College of Canada, Kingston, ON, Canada
vishva.shah@rmc.ca; cecile.malardier-jugroot@rmc.ca; manish.jugroot@rmc.ca
Gold nanoparticles have many applications in a variety of fields ranging from clinical chemistry to targeted drug
delivery. The size and the shape of the nanoparticles have proven to be important factors in determining the physical and
electronic properties of the nanoparticles, it is therefore important to use a template for the synthesis of highly ordered
gold nanoparticles. Poly(styrene-alt-maleic acid), SMA, is an amphiphilic alternating co-polymer which self assembles
in water into highly organized nanostructures and is a good candidate for use as a template. Indeed, this template has
been used successfully for an environmentally friendly synthesis of organic polymers (polypyrrole) as well as metal
nanoparticles(gold and platinum). Pyrrole was found to spontaneously polymerize within the confined hydrophobic
cavity of SMA whereas gold was found to form an atomically-thin gold monolayer on the outer hydrophilic surface of
SMA. In this study, we combined both of these results to control the interaction between SMA and gold in three ways
including sonication, altering the nature of the polymer and by using thiophene, a structurally similar molecule to
pyrrole, to exploit the well-known gold-sulphur bond to draw the gold(I) chloride precursor into the confined regions of
SMA. Since thiophene makes a strong bond with gold, we also studied the effect of this interaction on the interaction
between gold and SMA, which could make the hydrophobicity or hydrophillicity of the metal salt irrelevant. Moreover,
it was previously observed that the confined cavities of SMA also forced the direct reduction of hydrophobic metal salts
into platinum nanoclusters. The role and the effect of the interaction between the hydrophilic or hydrophobic cavities of
the template and the metal salt on the shape and size of the gold nanoparticles will be emphasized. The ability to
mediate the metal-polymer interaction by a coupling agent opens up many more possibilities for applications in
medicine, industry, and academia.
O18
Electrochemical Characterizations of Ultra-stable Self-assembled Monolayers of Nheterocyclic Carbenes on Gold
Zhe She,1,2 Mina R. Narouz,3 Christene A. Smith,3 Cathleen M. Crudden,3,4 J. Hugh Horton,3 and Heinz-Bernhard
Kraatz1,5,*
1
Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, ON,
2
Canada; Department of Chemistry and Chemical Engineering, Royal Military College of Canada,
3
4
Kingston, ON, Canada; Department of Chemistry, Queen's University, Kingston, ON, Canada; Institute
5
of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, Japan; Department
of Chemistry, University of Toronto, Toronto, ON, Canada
zhe.she@utoronto.ca; bernie.kraatz@utoronto.ca
A self-assembled monolayer (SAMs) is a layer of organic molecules assembled at surfaces often stabilized by high
binding affinities between the molecules and the surface substrate and by van der Waals interactions between adjacent
molecules. Film formed by the interaction of S-containing molecules and Au surfaces giving rise to strong Au-S
bonding has dominated this area of research since the first reports of Au-thiolate films by Nuzzo and Whitesides et al.
(1). Recently, N-heterocyclic carbenes based SAMs were reported to be more stable than traditional Au-S SAMs (2).
Here, we report the electrochemically characterization of these films, and provide information of their stability,
molecular density and electron transfer properties of carbene films.
(1) Bain, C. D.; Troughton, E. B.; Tao, Y. T.; Evall, J.; Whitesides, G. M.; Nuzzo, R. G. J. Am. Chem. Soc. 1989, 111,
321.
(2) Crudden, C. M.; Horton, J. H.; Ebralidze, I. I.; Zenkina, O. V.; McLean, A. B.; Drevniok, B.; She, Z.; Kraatz, H. -B.;
Mosey, N. J.; Seki, T.; Keske, E. C.; Leake, J. D.; Rousina-Webb, A.; Wu, G. Nature Chemistry 2014, 6, 409.
24
O19
Synthesis and Coordination of Amidines and Phosphaamidines Metal Complexes
Ramjee Kandel, Keith Huynh, Lauren Dalgliesh, Ruiyao Wang, and Philip G. Jessop*
kandel.ramjee@queensu.ca; jessop@queensu.ca
Transition metal complexes incorporating amidines and phosphaamidines ligands, have received less attention
and coordination chemistry is less known. They could interesting for their coordination chemistry and possibly of
catalysis.
Amidines are nitrogen containing bases where the unsaturated nitrogen is more active towards coordination and
can be easily protonated. Research in our laboratory has exploited the basicity of amidines as promoters of CO 2 fixation
to other products, while phosphaamidines are hybrid ligands containing a basic hard donor nitrogen atom and a soft
donor phosphorus atom. The design of acyclic phosphaamidine is attractive as the tunable Nimine should retain its
basicity while the P should preferentially coordinate to the most transition metals.
In this light, we have prepared a series of tunable acyclic amidines and phosphaamidines and tested their
coordinating abilities with Cu(I) and other transition metal ions. Amidines coordinated through only N imine leaving Namine
free while phosphaamidines coordinate through phosphorus and N imine depending upon the electronic and steric
properties of the phosphaamidines.
O20
Manganese(II) Dialkyl and Manganese(I) and (III) Hydride Complexes
Jeffrey S. Price, Preeti Chadha, and David J. H. Emslie*
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, Canada
pricej4@mcmaster.ca; emslied@mcmaster.ca
With a view towards the development of new organometallic precursors and reactivities for manganese metal atomic
layer deposition (ALD), the solid state structures and properties of [{Mn(μ-R)2}∞] (1; R = CH2SiMe3), [{Mn(R')(μR')2}2{Mn(μ-R')2Mn}] (2; R' = CH2CMe3), [Mn(R)2(dmpe)] (3; dmpe = 1,2-bis(dimethylphoshino)ethane), [{Mn(R')2(μdmpe)}2] (4), [{Mn(R)(μ-R)}2(μ-dmpe)] (5), [{Mn(R')(μ-R')}2(μ-dmpe)] (6), [{Mn(R)(μ-R)}2(μ-dmpm)] (7; dmpm =
bis(dimethylphoshino)methane), and [{Mn(R')(μ-R')}2(μ-dmpm)] (8) are reported. Syntheses for 1-4 have previously
been published, but the solid state structures and most properties of 2-4 had not been described. Compounds 5 and 6,
with a 1:2 dmpe:Mn ratio, were prepared by reaction of 3 and 4 with base-free 1 and 2, respectively. Compounds 7 and
8 were accessed by reaction of 1 and 2 with 0.5 or more equivalents of dmpm per manganese. An X-ray structure of 2
revealed a tetrametallic structure with two terminal and six bridging alkyl groups. The solid state structures of
bisphosphine-coordinated 3-8 revealed three distinct structure types: (a) monometallic [LMnX 2], (b) dimetallic
[X2Mn(µ-L)2MnX2], and (c) dimetallic [{XMn(µ-X)}2(µ-L)] (X = R or R'; L = dmpe or dmpm). Reactions of 1-8 with
H2 (25-120 °C) afforded manganese metal. By contrast, reaction of 1-8 with ZnEt2 (25 °C) afforded a ~ 1:1 Mn:Zn
alloy, accompanied in the case of dmpe-containing 3-6 by the formation of [Mn(dmpe)2(ethylene)(H)] (9). The solid
state structure of 9 is reported, along with oxidative addition reactivity leading to new manganese(III) hydride
complexes.
25
O21
Nitrene Transfer from Organic Azides Mediated by Metal Complexes of Bulky oPhenylenediamide Ligand
Pavel Zatsepin, Trevor Janes, and Datong Song*
pavel.zatsepin@mail.utoronto.ca; dsong@chem.utoronto.ca
The direct amination of C-H bonds is an area of great
interest to synthetic chemists1 as a means to access the
wide range of useful molecules with nitrogen-containing
functionalities2. One way to achieve this transformation is
to insert nitrenes into C–H bonds,3 where metal complexes
have been used to stabilize nitrenes and improve the
selectivity.4,5 In this presentation the reactivity of bulky
phenylenediamide (pda) complexes towards organic azides
in nitrene formation and transfer reactions will be
discussed . One example is shown below.
1.
2.
3.
4.
5.
Sharma, A.; Hartwig. J. F. Nature., 2015, 517, 600-604.
Hili, R.; Yudin, A. K., Nat. Chem. Biol., 2006, 2, 284-287.
Egger, J.; Carreira, E. M., Nat. Prod. Rep., 31, 451-453.
Hennessy, E. T.; Betley, T. A. Science., 2013, 340, 591-595.
Ramirez, T. A.; Zhao, B.; Shi, Y., Chem. Soc. Rev., 2012, 41, 931-942
O22
Solvent Stabilized Dinitrogen Trioxide as a Laboratory Reagent
Kristopher Rosadiuk and D. S. Bohle*
Department of Chemistry, McGill University, Montreal, QC, Canada
Kristopher.Rosadiuk@mail.mcgill.ca; Scott.Bohle@mcgill.ca
Dinitrogen trioxide (N2O3) is normally stable only under extremely cold temperatures, and quickly dissociates into NO
and NO2 upon warming. A little known fact is that N2O3 may be stabilized by dissolving it in organic solvents. This
presentation describes the handling of these solutions and explores some of the novel ways that it has been used in our
lab, such as the production of tertiary amine adducts and polymercury salts.
26
O23
Evaluation of Anisole-Substituted Boron Difluoride Formazanate Complexes for
Fluorescence Cell Imaging
Ryan R. Maar, Stephanie M. Barbon, Neha Sharma, Hilary Groom, Leonard G. Luyt, and Joe B. Gilroy*
rmaar@uwo.ca; joe.gilroy@uwo.ca
Fluorescent materials have been known for nearly a century, and are attractive targets for
scientists in research fields such as organic electronics, chemical sensing, and cell imaging.
Much of the research in the field of fluorescent materials has been devoted to four-coordinate
boron compounds with chelating, π-conjugated ligands.1 Recent advances by the Gilroy group
have focused on the synthesis of boron difluoride formazanate complexes (e.g., 1) which were
shown to exhibit tunable spectroscopic and redox properties.2 This presentation will describe a
systematic study designed to probe the effect of ortho-, meta-, and para-substitution patterns
of anisole rings bound to a boron difluoride formazanate scaffold. Based on its
straightforward, high-yielding synthesis and impressive fluorescence quantum yield, 1c was
chosen for fluorescence cell-imaging studies. The structural features, spectroscopic
characteristics and electrochemical properties of 1a−c, and the cell-imaging studies of 1c will
be discussed in detail during this presentation.
(1) Ulrich, G.; Ziessel, R.; Harriman, A. Angew. Chem. Int. Ed. 2008, 47, 1184−1201. (2)
Maar, R. R.; Barbon, S. M.; Sharma, N.; Groom, H.; Luyt, L. G.; Gilroy, J. B. Chem. Eur. J.
2015, DOI: 10.1002/chem.201502821.
O24
Pyrido[2,1-α]-isoindole as a Novel Ligand in Main Group and Transition Metal
Chemistry
Sean M. McDonald and Suning Wang*
sean.mcdonald@chem.queensu.ca; suning.wang@chem.queensu.ca
Pyrido[2,1-α]-isoindoles have been synthetically accessible since the 1960s. 1,2 However, very little investigation has
been made into their reactive capabilities. The majority of work has gone into studying cycloadditions with alkynes to
produce unique and polarized system.3,4 Due to its electronic structure, pyrido[2,1- α]-isoindole has nucleophilic
character at the 6-position, leading to great potential for use as a novel ligand in main group and transition metal
chemistry. The Wang group has already
showcased the adduct formation with
HB(C6F5)2 as an intermediate step towards
1,1-hydroboration.5 This work will detail the
coordination chemistry and novel reactivity
of pyrido[2,1-α]-isoindole with main group
elements and transition metals.
1. Fozard A., Bradsher C. K.; Tetrahedron Lett., 1966, 7, 3341. 2. Fozard A., Bradsher C. K.; J. Org. Chem., 1967, 32,
2966. 3. Kajigaeshi S., Mori S., Fujisaki S., Kanemasa S.; Bull. Chem. Soc. Jpn., 1985, 58, 3547. 4. Mitsumori T.,
Bendikov M., Dautel O., Wudl F., Shioya T., Sato H., Sato Y.; JACS, 2004, 51, 16793. 5. Yang D.-T., Mellerup S. K.,
Wang X., Lu J.-S., Wang S.; Angew.Chem.Int.Ed., 2015, 54, 5498.
27
O25
Bis-Carbene-Stabilized Phosphorus Cations
Justin F. Binder, Ala’aeddeen Swidan, Martin Tang, Jennifer H. Nguyen, and Charles L. B. Macdonald *
binderj@uwindsor.ca; cmacd@uwindsor.ca
Phosphamethine cyanine dyes are landmark molecules for main group chemistry in that they provided the first concrete
evidence of 3p-2p π-bonding.1 In spite of this historical relevance, chemistry involving these low-valent phosphorus
compounds remains underexplored. Our group discovered that the reaction between a triphosphenium salt and carbenes
is a safe, convenient route to such species.2 Investigations into their syntheses, properties and reactivity are presented.
1 P. Jutzi, Angew. Chem. Int. Ed., 1975, 14, 232–245.
2 B. D. Ellis, C. A. Dyker, A. Decken and C. L. B. Macdonald, Chem. Commun., 2005, 1965–1967.
O26
Engineered Designer Monomers: The Path to Light and Moisture Stable
Polystannanes
Jeffrey Pau and Daniel Foucher*
Department of Chemistry and Biology, Ryerson University, Toronto, ON, Canada
j2pau@ryerson.ca; daniel.foucher@ryerson.ca
This work continues an investigation into the utility of covalently attached light absorbing chromophores to protect the
light sensitive Sn-Sn backbone of polystannanes. Here the UV absorbing azobenzene “antenna” is incorporated into a
polymerizable tin dihydride monomer that may lead to interesting homo- and copolystannane materials. Additionally,
the flexible nature of the attached UV chromophore is such that it can adopt 5-coordinate geometry at Sn to further
protect the sensitive Sn-Sn polymer bonds from nucleophilic attack. In this work, we present syntheses of azostannyl
compound 5 achieved through a Williamson ether synthesis.
Compound 5 is then sequentially chlorinated to the mono- 6
and dichlorostannane 7. Compound 8 was then obtained by
hydrogenation of 7 with LiAlH4. The azo-stannyl monomer 8
was then reacted with a suitable transition metal catalyst that
promoted dehydropolymerization to the polystannane 9. All
structures were confirmed by NMR (1H, 13C, 119Sn, HSQC)
and in the case of 5 and 6, an X-ray crystal structure analysis.
The UV behaviour of the azo-stannyl compounds were also
probed by UV-Vis spectroscopy. Investigations show that the
cis- (n-p*) and trans- (p-p*) light switching characteristics of
azobenzene are preserved in the stannyl compounds.
28
O27
N-Heterocyclic Carbene Stabilized Ag Nanoparticles
Iraklii I. Ebralidze1 and Heinz-Bernhard Kraatz1,2*
1
Department of Physical and Environmental Sciences, University of Toronto, Scarborough, ON, Canada;
Department of Chemistry and Chemical Engineering, Royal Military College, Kingston, ON, Canada
iraklii.ebralidze@utoronto.ca; bernie.kraatz@utoronto.ca
2
Metal nanoparticles (NPs) are a focus of interest because of their unique properties and thus huge potential in science
and engineering. Silver nanoparticles (AgNPs) as well as silver in ionic form, are known to possess antimicrobial
effects. AgNPs are known to interact with heavy metal ions such as Hg(II), Hg(I), Pb(II), and Cd(II) showing significant
growth in size upon their incorporation and therefore can be used for drinking water purification. 1 Moreover, silver NPs
can be synthesized and modified with various chemical functional groups which allow them to be conjugated with
antibodies, ligands, and drugs of interest and thus opening a wide range of potential applications in biotechnology,
magnetic separation, and pre-concentration of target analytes, targeted drug delivery, and vehicles for gene and drug
delivery and more importantly diagnostic imaging. 2 Even though tremendous number of applications, synthetic routes
for AgNPs are limited to the reduction of Ag+ in presence of stabilizing/capping reagents such as (I) nonionic
surfactants (poly(vinyl pyrrolidone, Triton X-100 ), (II) citrate anions, (III) thiols, or their mixtures. From this list only
thiols form strong bonds with AuNPs and allow further functionalization to achieve desired modern architectures.
Crudden et al.3 have recently shown that thiols anchored to gold surfaces can be substituted by N-heterocyclic carbenes
(NHC) due to formation of much stronger covalent Au-NHC bond. On the other hand, deprotonation of azolium salts
(NHC precursors) using a silver base (or simultaneously a silver salt and a base) has been the most widely used method
in the syntheses of NHC complexes of silver. Taking this into mind, we developed a route of formation of AgNPs
starting from NHC-Ag complexes. This route results in AgNPs stabilized by covalently bounded carbenes.
1. M.S. Bootharaju, T. Pradeep, J. Phys. Chem. C. 114(18), 2010, 8328–8336. 2. V.V. Mody, R. Siwale, A. Singh, H.R.
Mody. J.Pharm. Bioallied Sci. 2(4), 2010, 282-289. 3. Cathleen M. Crudden et al. Nature Chem. 6, 2014, 409–414.
O28
Iterative, Protecting Group Free Suzuki-Miyaura Coupling of Enantioenriched
Polyboronates
C. Ziebenhaus,1 Jason P. G. Rygus,1 K. Ghozati,1 P. J. Unsworth,1 S. Voth,1 Y. Maekawa,1 C. M. Crudden,*,1 and
M. Nambo2
1
2
Department of Chemistry, Queen’s University, Kingston, ON, Canada; Nagoya University, Japan
jason.rygus@chem.queensu.ca; cathleen.crudden@chem.queensu.ca
The Suzuki-Miyaura cross-coupling is among the most widely used reactions in
chemical synthesis. In particular, it has found wide applicability in the construction of
biaryl or polyene scaffolds, and has been proposed as the key reaction for the modular,
automated assembly of such structural motifs1. Such a process relies on the use of
protecting groups to modulate the activity of various C-B bonds, and thus requires
costly, inefficient protection and deprotection steps for each bond forming sequence.
Herein we describe a significant advancement in the field of iterative cross-coupling
of polyborylated substrates containing aromatic, primary aliphatic and second
aliphatic C-B bonds2 to generate enantioenriched, multiply arylated structures without
the use of boron protecting groups. We demonstrate chemoselective cross-coupling
based solely on the intrinsic differences in reactivity imparted by the nature of the C-B
bond.
1
Woerly E.M., Roy J. & Burke M.D., Nature Chem. 2014, 6, 484
2
Imao D., Glasspoole B.W., Laberge V.S. & Crudden C.M. J. Am. Chem. Soc. 2009, 131, 5024
29
O29
Chan-Lam Coupling Using a Copper(II) Complex with a Sulfonated Diketimine
Ligand
Valérie Hardouin Duparc and Frank Schaper*
Département de chimie, Université de Montréal, Montréal, QC, Canada
valerie.hardouin.duparc@gmail.com; frank.schaper@umontreal.ca
Chan-Lam coupling is a well-known cross-coupling reaction between an aryl boronic
acid and an alcohol or an amine in presence of copper(II) to form a C-O or C-N
bond.1 While environmentally friendly and economic, several aspects of Chan-Lam
couplings can still be optimized: reaction conditions often need to be adapted for the
substrate, stoichiometric amounts of copper are sometimes required and presence of
base is normally necessary.2
We recently synthetized copper complexes based on sulfonated
diketimine ligands,3 and studied their structural features and stability. The
obtained complexes were then tested in Chan-Lam coupling and proved to
work under mild condition and to be applicable to a variety of amine
substrates.
1
(a) Chan, D. M. T.; Monaco, K. L.; Wang, R.-P.; Winters, M. P. Tetrahedron Lett. 1998, 39, 2933. (b) Evans, D. A.;
Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937. (c) Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.;
Winters, M. P.; Chan, D. M. T.; Combs, A. Tetrahedron Lett. 1998, 39, 2941.
2
(a) Ley, S. V.; Thomas, A. W. Angew. Chem. Int. Ed. 2003, 42, 5400 (b) Allen, S. E.; Walvoord,R. R.; Padilla-Salinas,
R.; Kozlowski, M. C. Chem. Rev. 2013, 113, 6234.
3
Rajendran, N. M.; Reddy, N. D. Polyhedron 2014, 72, 27.
O30
Stable Organopalladium(IV) Aryldiazenido Complexes
David Armstrong,1 Marzieh Daryanavard,1 Alan J. Lough,2 and Ulrich W. Fekl*,1
1
2
University of Toronto Mississauga, Mississauga, ON, Canada; University of Toronto, Toronto, ON,
Canada
dayv.armstrong@utoronto.ca; ulrich.fekl@utoronto.ca
The usefulness of palladium complexes as catalysts in organic synthesis,
for a range of C-C and C-X coupling reactions, is well recognized.1 The
2010 Nobel Prize in Chemistry was awarded to Heck, Negishi, and
Suzuki for their work on palladium catalyzed cross-coupling reactions.2
Mechanistically, the vast majority of catalytic cycles involve a
Pd(0)/Pd(II) redox couple.1,3 While there have been some recent reports
of the involvement of Pd(III) and Pd(IV) 4 in some catalytic cycles, much
less is known about the catalytic potential of Pd(II)/Pd(IV) redox pairs. 5
We have demonstrated the synthesis and characterization of the first
palladium(IV) aryldiazenido complexes, formed by the oxidation of
(Tp*)PdMe2 (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) using
aryldiazonium salts. Thermolysis of these compounds leads to substituted
biphenyls via C-C coupling. Synthesis and reactivity will be discussed, as well as implications for palladium catalysis
involving high oxidation states of palladium.
1
Negishi, E. Handbook of Organopalladium Chemistry for Organic Synthesis; John Wiley & Sons: NJ, 2002.
2
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2010/.
3
(a) van Leeuwen, P. W. N. M. Homogeneous Catalysis: Understanding the Art; Kluwer: The Netherlands, 2004.
4
(a) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (b) Xu, L.-M.; Li, B.-J.; Yang, Z.; Shi, Z.-J. Chem.
Soc. Rev. 2010, 39, 712. (c) Canty, A. J. Dalton Trans. 2009, 10409.
5
(a) Khusnutdinova, J. R.; Qu, F.; Zhang, Y.; Rath, N. P.; Mirica, L. M. Organometallics 2012, 31, 4627. (b)
Chuang, G. J.; Wang, W.; Lee, E.; Ritter, T. J. Am. Chem. Soc. 2011, 133, 1760.
30
O31
Selective C(sp2)-O Bond Formation from Palladium Complexes by Using a Green
Oxidant
Ava Behnia, Johanna M. Blacquiere*, and Richard J. Puddephatt *
abehnia@uwo.ca; johanna.blacquiere@uwo.ca; pudd@uwo.ca
Palladium-catalyzed cross-coupling reactions have revolutionized the ability to form C–heteroatom bonds as well as CC bonds. Generation of oxygen containing compounds via C-O reductive elimination are less common and not well
understood. However, C-O bond forming reductive elimination reactions might be very beneficial for designing more
effective and environmentally benign catalytic reactions where H 2O2 is used as oxidant. Recently, Mirica et. al. have
introduced an example of selective C(sp2)-O bond forming reaction from a Pd(IV) complex with a tridentate N-donor
ligand.2 Alternatively, Sanford et. al. observed selective C(sp3)-O reductive elimination with a Pd complex ligated by a
bidentate N-donor ligand.3 These observations suggest that the nature of the ligand plays a role in controlling selectivity
of the bond forming step. We have targeted a Pd(II) complex with a bidentate N-donor and a hydrocarbon ligand that
can coordinate to the metal center through C(sp 2) and C(sp3) centers. We have treated the Pd(II) complex with different
kinds of oxidants to probe the ability to form stable palladium(IV) complexes or to form new palladium(II) complexes
by sequential oxidative addition/reductive elimination reactions. Use of H 2O2 as the oxidant gives a very rare example
of C-O bond formation by oxygen atom insertion into an arylpalladium bond. In our system the Pd-C(sp2) bond is more
reactive than the Pd-C(sp3) bond towards reductive elimination reactions.
(1) Hassan, J.; Sévignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev., 2002, 102, 1359. (2) Qu, F.;
Khusnutdinova, J. R.; Rath, N. P.; Mirica, L. M. Chem. Commun., 2014, 50, 3036. (3) Camasso, N. N.; PérezTemprano, M. H.; Sanford, M. S. J. Am. Chem. Soc., 2014, 136, 12771.
O32
Tuning the Steric and Electronic Properties of Iron-Based Catalysts Using
Modular Phosphine Moieties
Samantha A.M. Smith, Alan J. Lough, and Robert H. Morris*
samanthaam.smith@mail.utoronto.ca; robert.morris@utoronto.ca
ν(CO) (Cm-1)
1980
The asymmetric hydrogenation (AH)
of ketones is an efficient method for
1975
producing enantio-enriched alcohols
1970
for the use in industrial processes.i
1965
The last decade has proven that the
use of earth-abundant metals as
1960
opposed to precious metals is viable
1955
for the reduction of polar double
i-iii
1950
bonds. Our group has focused on
the use of iron in catalysis for both
1945
asymmetric transfer hydrogenation
1940
(ATH) and AH.iv Our most recently
130
140
150
160
170
180
v,vi
Cone Angle (deg)
developed third generation catalysts
are highly efficient for the reduction
of ketones via ATH, but not entirely understood. We became interested in how the steric and electronic properties of the
phosphorus moieties alter catalytic results and thus we will discuss how the systematic modification of the substituents
at one phosphorus alter the catalyst structures and their activities and selectivities.
i
R. H. Morris, Acc. Chem. Res. 2015, 48, 1494; ii Ohkuma, Takeshi, et al. JACS., 2006, 128, 8724; iii T. Ikariya, A. J.
Blacker, Acc. Chem. Res., 2007, 40, 1300; iv P. E. Sues, K. Z. Demmans, R. H. Morris, Dalton Trans., 43, 2014, 7650; v
W. Zuo, A. J. Lough, Y. F. Li, R. H. Morris, Science, 2013, 342, 1080; vi S. A. M. Smith, R. H. Morris, Synthesis, 2015,
47, 1775
31
O33
Intercalation of Coordinatively-Unsaturated FeIII Ion within Interpenetrated
MOF-5
Rebecca J. Holmberg, Thomas Burns, Samuel M. Greer, Libor Kobera, Sebastian A. Stoian, Ilia Korobkov,
Stephen Hill, David L. Bryce, Tom K. Woo, and Muralee Murugesu*
rholmber@uottawa.ca; m.murugesu@uottawa.ca
Despite the potential that has clearly been displayed by metal substitution within MOF-5, there have not yet been any
examples of metal addition to the structure outside of the Zn4O SBU. This is a worthwhile endeavor, especially
considering the already remarkable improvements to the properties of MOF-5 that have been accessed through simple
metal substitution.1 Thus, we set out to explore the addition of a coordinatively unsaturated Fe III metal site to the
framework. This new structure, Fe III-iMOF-5,2 is the first example of an interpenetrated MOF linked through
intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by
extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its
interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed Fe III,
while DFT calculations were employed to ascertain the unique pentacoordinate architecture around the Fe III ion.
Interestingly, this is also the first crystallographic evidence of pentacoordinate Zn II within the MOF-5 SBU. This new
MOF structure displays the potential for metal site addition as a framework connector, thus, creating further opportunity
for the innovative development of new MOF materials.
1 (a) Botas, J. A.; Calleja, G.; Sánchez-Sánchez, M.; Orcajo, M. G. Langmuir 2010, 26, 5300.; (b) Brozek, C. K.;
Dincă, M. Chem. Sci. 2012, 3, 2110.; (c) Brozek, C. K.; Dincă, M. J. Am. Chem. Soc. 2013, 135, 12886.; (d) Brozek,
C. K.; Miller, J. T.; Stoian, S. A.; Dincă, M. J. Am. Chem. Soc. 2015, 137, 7495.; (e) Brozek, C. K.; Michaelis, V.
K.; Ong, T.-C.; Bellarosa, L.; López, N.; Griffin, R. G.; Dincă, M. ACS Cent. Sci. 2015, 1, 252.
2 Holmberg, R. J.; Burns, T.; Greer, S. M.; Kobera, L.; Stoian, S. A.; Korobkov, I.; Hill, S.; Bryce, D. L.; Woo, T.
K.; Murugesu, M. J. Am. Chem. Soc. 2015, ja-2015-10584t.
O34
Towards Modeling the Active Site of Photosystem II: New Structural Motifs in
Mn/Ca Chemistry from the Use of Salicylhydroxime
Alysha A. Alaimo,1 Simon J. Teat,2 George Christou,3 and Theocharis C. Stamatatos*,1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; Advanced Light Source,
3
Lawrence Berkeley National Laboratory, Berkeley, CA, USA; Department of Chemistry, University of
Florida, Gainesville, Florida, USA
aa08mi@brocku.ca; tstamatatos@brocku.ca
Toward the synthesis of new structural models of the oxygenevolving complex (OEC) within Photosystem II, some of the most
crucial challenges to confront are: (i) the Mn4Ca metal
stoichiometry, (ii) the extended, distorted cubane conformation, (iii)
the stability of high oxidation states for the Mn ions, and (iv) the
choice of the ancillary bridging ligand(s). With this in mind, we
have chosen to employ salicylhydroxamic acid (shaH2, Scheme 1), a photosynthetically
effective group, as a means of obtaining new molecular species containing both Mnn+
(n>2) and Ca2+.1 Ligand shaH2 can potentially undergo a metal-assisted amide-iminol
tautomerism, and thus transform to salicylhydroxime (shiH3); the latter is an oximatebased ligand with four coordination sites available for binding to both high oxidation state
Mn and Ca2+ metal centers. We here present the synthesis, structural, and physicochemical
properties of a series of new heterometallic Mn/Ca complexes with interesting topologies
and novel molecular motifs (Figure).
1
A. A. Alaimo, D. Takahashi, L. Cunha-Silva, G. Christou, Th. C. Stamatatos, Inorg.
Chem. 54, 2137, 2015
32
O35
Single Molecule Magnet (SMM)
Munendra Yadav and Scott Bohle *
Munendra.yadav@mcgill.ca; david.bohle@mcgill.ca
Single Molecule Magnets (SMM) is a class of molecular compounds which shows
supermagnetic behaviour below a certain temperature called as the blocking temperate (TB).
These complexes act as nanomagnets, in which every single molecule behaves like an
independent magnet. The basic requirement to show SMM behaviour is that the complex
should have negative uni-axial magnetic anisotropy (D) and a non zero spin ground state (S).
These two parameters combine to give an energy barrier by which slow relaxation of
magnetization can take place. This energy barrier for integral spin is calculated by U eff =
│D│S2 and for half integral spin Ueff = │D│(S2-1/4). The negative uni-axial anisotropy (D ˂
0) removes the degeneracy of ground spin states (M S) = ±S.
Interest in lanthanide ions has been revived and 4f coordination compounds have been
extensively investigated for their single-molecule magnet (SMM) and single-ion magnet
(SIM) properties. The large spin multiplicity and large magnetic anisotropies of
lanthanides ions in the ground state plays a key role to get the SMM behaviour. Strong
single ion anisotropy of lanthanides and flexibility in anisotropy is another advantage by
which it is easy to design the ligand so that it can create the ligand field anisotropy.
Munendra Yadav, Valeriu Mereacre, Sergei Lebedkin, Manfred M. Kappes, Annie K.
Powell, and Peter W. Roesky “Mononuclear and Tetranuclear Compounds of Yttrium and Dysprosium ligated by a
Salicylic Schiff-Base Derivative: Synthesis, Photoluminescence and Magnetism” Inorg. Chem. 2015, 54, 773-781.
O36
Ligand Effects in Copper-Catalyzed Aerobic Oxygenation of Phenols
Laura Andrea Rodríguez Solano,1 Jean-Phlip Lumb,2 and Xavier Ottenwaelder1*
1
XoRG, Department of Chemistry and Biochemistry, Concordia University, Montreal, QC, Canada;
lanrosol@gmail.com; dr.x@concordia.ca
2
Tyrosinase is a ubiquitous copper-containing enzyme that converts phenols into ortho-quinones. Its active site contains
two His3-Cu centres that activate O2 in the form of a side-on peroxo dicopper(II) species, P.1 Biomimetic studies have
shown that polyamine ligands can control the reactivity between Cu(I) and O 2, favouring different coordination modes
and CunO2 species.2 Recently, the Lumb group reported an efficient tyrosinase-like catalytic system capable of
converting phenols into ortho-quinones under aerobic conditions.4 Our mechanistic study demonstrated the involvement
of a P species in the catalytic cycle.5 The present work showcases systematic variations of the ligand used in this
catalytic system, with 4-tert-butylphenol as model
substrate. We correlate the catalytic efficiency at room
temperature with the nature of the Cu2O2 species forming
at -80°C, and show that only ligands that can
accommodate a P intermediate lead to decent catalysis.
We propose plausible grounds to explain this correlation.
1.
2.
3.
4.
5.
Solomon, E. I. et al. Chem. Rev. 114, 3659–3853 (2014).
Mirica, L. M., Ottenwaelder, X. & Stack, T. D. P. Chem Rev 104, 1013–1046 (2004).
Mirica, L. M. et al. Science 308, 1890–1892 (2005).
Esguerra, K. V. N., Fall, Y. & Lumb, J.-P. Angew. Chem. Int. Ed. 53, 5877–5881 (2014).
Askari, M. S., Esguerra, K. V. N., Lumb, J.-P. & Ottenwaelder, X. Inorg. Chem. 54, 8665–8672 (2015).
33
O37
1,2-Diphosphonium Dication : A Strong P-Based Lewis Acid in Frustrated Lewis
Pair Activations of B-H, Si-H, C-H and H-H Bonds
Julia M. Bayne, Michael H. Holthausen, Ian Mallov, Roman Dobrovetsky, and Doug W. Stephan *
julia.bayne@mail.utoronto.ca; dstephan@chem.utoronto.ca
The heterolytic splitting of dihydrogen (H2) by main group frustrated Lewis pairs (FLPs) remains a landmark
achievement in Lewis acid and FLP chemistry. FLPs used for small molecule activation typically exploit boranes,
alanes, or tricoordinate carbon- or silicon-centered cations as main group Lewis acids.1 Exploring electron deficient
compounds of group 15, our group demonstrated the remarkable catalytic activity of the highly electrophilic phosphorus
cation (EPC) [(C6F5)3PF]+ and the phosphonium dication [(SIMes)Ph2PF]2+ in a variety of Lewis acid-mediated
transformations.2 Although EPCs have been exploited as Lewis acid catalysts, examples of P-based Lewis acids in FLPtype reactions are scarce. To this end, our group reported the direct activation of H 2 with a triphosphabenzene
derivative3 and olefin hydrogenation with the phosphonium cation [(C6F5)3PF]+ and sterically encumbered aryl amines.4
In this presentation, the synthesis and reactivity of a robust and highly Lewis acidic 1,2-diphosphonium dication
[(C10H6)(Ph2P)2]2+ will be discussed. In combination with phosphorus Lewis bases, the remarkable hydridophilicity of
this dication was demonstrated through its ability to activate B-H, Si-H, C-H and H-H bonds.5
(1) D. W. Stephan and G. Erker, Angew. Chem. Int. Ed., 2015, 54, 6400-6441. (2) J. M. Bayne and D. W. Stephan,
Chem. Soc. Rev., 2015, DOI: 10.1039/C5CS00516G. (3) L. E. Longobardi et al., J. Am. Chem. Soc., 2014, 136, 1345313457. (4) T. vom Stein et al., Angew. Chem. Int Ed., 2015, 54, 10178-10182. (5) M. H. Holthausen, J. M. Bayne, I.
Mallov, R. Dobrovetsky and D. W. Stephan, J. Am. Chem. Soc., 2015, 137, 7298-7301.
O38
Progress in Boro-cation Catalysis for Hydrofunctionalization
Patrick Eisenberger* and Cathleen M. Crudden*
Department of Chemistry, Queen's University, Kingston, ON, Canada
patrick.eisenberger@chem.queensu.ca; cathleen.crudden@chem.queensu.ca
Cationic, 3-coordinate boron compounds have recently stepped into the limelight as promising non-metal-based Lewis
acidic catalysts for organic synthesis.[1] Here we present our
progress in catalyst design using meso-ionic carbene-stabilized
borenium as well as DABCO-borenium ions for mild
hydrofunctionalization of unsaturated organic molecules with
hydrogen and borane.[2,3] Mechanistic investigations suggest
that both these processes occur by distinctly different pathways
involving common motifs of Lewis-base supported boreniumions participating in bond activation and Lewis base supported
boranes as the reductant.
[1]
T. S. De Vries, A. Prokofievs, E. Vedejs Chem. Rev. 2012,
112, 4246. [2] P. Eisenberger, A. M. Bailey, C. M. Crudden J.
Am. Chem. Soc. 2012, 134, 17384. [3] P. Eisenberger, B. P.
Bestvater, E. C. Keske, C. M. Crudden Angew. Chem. Int. Ed. 2015, 54, 2467.
34
P1
Complexation of Fe(II) and Fe(III) with the Tau Protein
Soha Ahmadi,1,2 Iraklii I. Ebralidze,1 Zhe She,1 and Heinz-Bernhard Kraatz*1,2
1
2
Canada; Department of Chemistry, University of Toronto, Toronto, ON, Canada
soha.ahmadi@mail.utoronto.ca; bernie.kraatz@utoronto.ca
Tau is a protein that is associated with the stabilization of microtubules. A number of isoforms have been described in
the literature and all have binding domains that bind to microtubules. (1) Hyperphosphorylation of tau catalyzed by
protein kinases disrupts the interaction between tau and the microtubules, which in turn destabilizes the tubules leading
to decomposition into their building blocks a- and b-tubulins. (2) Hyperphosphorylation of tau then leads to aggregation
and formation of neurofibrillary tangles, one of the hallmarks of Alzheimer’s disease. Metal ions appear to play a vital
role and experimental results have shown increased levels of Fe, Cu, and Zn are associated with neurofibrillary tangles.
(3) Previously we have demonstrated that Cu(II) and Zn(II) can interact with tau and with phosphorylated tau (p-tau)
(4). Here we investigate the interaction of Fe(II) and Fe(III) with tau, p-tau and fragment peptides in an effort to further
our understanding of metal-tau interactions.
1. Frost, B., Götz, J., Feany, M.B. Connecting the dots between tau dysfunction and neurodegeneration . 2015, 25, 4653;
2. Krüger, .L; Mandelkow, E.M. Tau neurotoxicity and rescue in animal models of human Tauopathies. Current
Opinion in Neurobiology. 2016, 36, 52-58;
3. Ayton S., Lei P., Bush A.L. Biometals and Their Therapeutic Implications in Alzheimer’sDisease. Neurotherapeutics.
2015, 12, 109-120;
4. Martic, S.; Rains, M. K.; Kraatz, H.-B. Probing copper/tau protein interactions electrochemically. Anal. Biochem.
2013, 442, 130-137
P2
New Classes of Ferromagnetic Materials with Exclusively End-on Azido Bridges:
From Single- to 2D- Molecular Magnets
Dimitris I. Alexandropoulos,1 Luís Cunha-Silva,2 Albert Escuer,3 and Theocharis C. Stamatatos*1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; REQUIMTE & Department of
3
Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal; Departament de
Quimica Inorganica, Universitat de Barcelona, Barcelona, Spain
da12he@brocku.ca; tstamatatos@brocku.ca
A new, flexible synthetic route which does not require the co-presence of any organic
chelating/bridging ligand but only the “key” precursor Me 3SiN3 has been discovered
and led to a new class of inorganic materials bearing exclusively end-on azido bridges;
the reported 3d-metal clusters and coordination polymers exhibit ferromagnetic,
single-molecule magnetism (Figure) and long-range magnetic ordering properties.1
[1] D. I. Alexandropoulos, L. Cunha-Silva, A. Escuer, and Th. C. Stamatatos, Chem
Eur. J., 2014, 20, 13860.
II
Figure. χM'' vs. T plot for a [Co 7]
complex discussed in this work.
35
P3
Synthesis and Characterization of a Family of [ReBr(CO)3(NN)]-Polyoxometalate
Covalent Hybrids
Thomas Auvray, Marie-Pierre Santoni, and Garry Hanan*
Département de chimie, Université de Montréal, Montréal, QC, Canada
thomas.auvray@umontreal.ca; garry.hanan@umontreal.ca
The elaboration of hybrid systems combining the
intrinsic properties of its subcomponents is a widely
used approach in modern chemistry. Being interested
in the design of efficient light harvesting species to
convert solar energy into chemical energy, we decided
to combine the well-known [Re(CO)3Br(bpy)]
photosensitizer with polyoxometalates, a family of
anionic oxoclusters known for its electron reservoir
properties.1 A family of polypyridine ligands
covalently grafted on a Dawson type polyoxometalate
and its use as ligands to prepared the corresponding
Re(I) complex is presented.
1
M.-P. Santoni et al. , Dalton Trans., 2014, 43, 69906993
P4
Characterization of Cross-Coupling Reactions of Simple Iron Salts with Phenyl
Nucleophiles
Stephanie H. Carpenter and Michael L. Neidig*
Department of Chemistry, University of Rochester, Rochester, NY, USA
scarpen7@ur.rochester.edu; neidig@chem.rochester.edu
Iron-catalyzed C-C cross-coupling systems have been known since the 1970s1, yet there is limited mechanistic
understanding of these systems. Simple iron salts are inexpensive and nontoxic, and are known to have short reaction
times and mild reaction conditions. Hence, simple iron salts are attractive starting materials for cross-coupling systems.
Previous work in the group involves the isolation and characterization of a homoleptic tetramethyliron(III) ferrate
complex from catalytically relevant iron salt, solvent, and methylmagnesium bromide. Further studies showed the
homoleptic tetramethyliron(III) ferrate complex to be an intermediate in the reduction pathway of FeCl 3 and MeMgBr.
Current efforts are being placed on the isolation of intermediates formed during the reaction from simple iron salts and
various phenyl nucleophiles. Electron paramagnetic resonance (EPR) and Mössbauer spectroscopy have shown the
intermediates formed from simple iron salts and phenyl nucleophiles to be different from the methyl reduction pathway.
1.
2.
Tamura, M.; Kochi, J. K. J. Am. Chem. Soc. 1971, 93, 1487.
Al-Afyouni, M. H.; Fillman, K. L.; Brennessel, W. W.; Neidig, M. L. J. Am. Chem. Soc. 2014, 136, 15457.
36
P5
d10 Nickel Difluorocarbenes and their Cycloaddition Addition Reactions with
Tetrafluoroethylene
Alex L. Daniels, Daniel J. Harrison*, Ilia Korobkov, and R. Tom Baker*
adani088@uottawa.ca; dharris2@uottawa.ca; rbaker@uOttawa.ca
We report the first isolable nickel difluorocarbene complexes {NiP 2[P(OMe)3](=CF2); P2 = Ph2P(CH2)2PPh2 (1); P2 = 2
P(OMe)3 (2)}, which are also the only examples of formally d 10 metal fluorocarbenes. These electron-rich [Ni0]=CF2
complexes react with tetrafluoroethylene (TFE) to yield rare perfluorometallacyclobutanes [NiP 2(κ2-CF2CF2CF2-), 3 and
4], with potential relevance to fluoroalkene metathesis and polymerization. Kinetic experiments establish that the
reactions of the new [Ni]=CF2 compounds with TFE are considerably faster than the analogous reactions of their
previously reported [Co]=CF2 counterparts. Further, we show that TFE addition to 2 is a dissociative process, in
contrast to [Co]=CF2, which reacts with TFE in an associative fashion. Finally, preliminary reactivity of a [Ni](κ 2CF2CF2CF2-) complex (3) is described.
P6
Exploring the Water-Tolerance of Ruthenium Metathesis Catalysts
Adrian G. G. Botti and Deryn E. Fogg*
University of Ottawa, Centre for Catalysis Research and Innovation, Ottawa, ON, Canada
abott010@uottawa.ca; deryn.fogg@uottawa.ca
The dominant catalysts in current use for olefin metathesis are “second-generation” catalysts bearing an N-heterocyclic
carbene (NHC) ligand, particularly the Grubbs and Hoveyda catalysts (Chart 1). These catalysts are widely regarded as
tolerant toward air and moisture. Indeed, Cazin and co-workers recently reported that turnover numbers up to 7,000
could be attained in non-degassed solvents in RCM of a 1,1-disubstituted olefin using HII.1 On deliberate addition of
water, however, maximum conversions were halved. Here we explore the basis of this behaviour, for both GII and HII.
Specifically, we describe the impact of added water on catalytic productivity with a more typical, ,-vinylic substrate;
we examine reactions of the off-cycle species (precatalyst and resting state; Chart 1) and active catalysts with water,
with a particular focus on the nature of the side-products generated. Finally, we also explore the stability of Ruthenium
species potentially generated via reactions with water.
Chart 1. (a) The dominant olefin metathesis catalysts; (b) Mechanism highlighting key catalytic species studied for GII.
(a)
(b)
[1] S. Guidone, O. Songs, F. Nahra, C. S. J. Cazin, ACS Catal. 2015, 5, 2697-2701.
37
P7
The Synthesis and Coordination Chemistry of 3,3’-Disubstituted-2,2’-Bipyridine
Ligands – Dimers, Trimers, Tetramers, and 1-D Chains
Marnie Edwardson, Nicholas J. Hurley, and Melanie Pilkington*
me10wm@brocku.ca; mpilkington@brocku.ca
Bipyridines are a unique class of compounds that are very prevalent in the fields of surpramolecular and coordination
chemistry. Out of six possible regioisomers, 2,2’-bipyridine ligands are the most exploited. However, examples of 3,3’disubstituted-2,2’-bipyridines are less common and have not yet realized their full potential in the field of coordination
chemistry to date1.
In recent years we have pursued the synthesis and coordination chemistry of polydentate 3,3’-substituted-2,2’-pyridine
ligands (1)2 and (2)3 with appended pyridine and pyrazine heterocycles respectively. More recently we have targeted the
preparation of a new ligand (3) with appended oxadiazole-pyridyl heterocycles. The preparation of these ligands
together with magnetostructural studies of selected coordination complexes will be presented.
1
C.R. Rice, S. Onions, N. Vidal, J.D. Wallis, M.C. Senna, M. Pilkington, & H. Stoeckli‐Evans, Eur. J. Inorg.
Chem. 2002, 8, 1985-1997,2 N.J. Hurley, J.J. Hayward, J.M. Rawson, M. Murrie, & M. Pilkington, Inorg. Chem. 2014,
53, 8610-8623, 3 N.J. Hurley, J.M. Rawson, & M. Pilkington, Dalton Trans. 2015, 44, 1866-1874.
P8
Synthesis and Reactivity of Phosphinimine Phosphine Staudinger Products
Louie Fan and Doug W. Stephan*
louie.fan.09.chem@gmail.com; dstephan@chem.utoronto.ca
Frustrated Lewis pairs (FLP) have gained significant attention in the chemical community for their use in the metal-free
activation of small molecules, such as H2, CO2, and NO. The premise for Lewis bases and Lewis acids to have weakly
or nonbonding interactions has been thoroughly investigated in both interand intramolecular FLP systems. Recently, our group reported the reactivity
of various phosphinimine borane1 and borenium2 Staudinger derived
products for FLP-type chemistry.
In this work, borane-stabilized phosphorus azide, iPr2P(BH3)N3, is reacted
with a series of phosphorus alkynes, R12PCCR2 (R1 = t-Bu, iPr, Ph, R2 = Ph,
Cy, t-Bu), to generate a family of new phosphinime phosphine products
(Fig. 1). The preparation, characterization and reactivity of a series of
phosphinimine phosphine Staudinger products are explored herein.
1
R.L. Melen, A.J. Lough, D.W. Stephan,; Dalton Trans., 42, 8674-8683. 2M.H. Holthausen, I. Mallov, D.W.
Stephan,; Dalton Trans., 43, 15201-15211.
38
P9
Study of Bis-peptide Derivatives of Ferrocenoyl Histidine Including
Electrochemical and Metal Ion Binding Studies
Annaleizle Ferranco and Heinz-Bernhard Kraatz*
Canada
annaleizle.ferranco@mail.utoronto.ca; bernie.kraatz@utoronto.ca
Zinc ions are essential for a variety of biological functions in proteins. In some case, Zn(II) plays a structural role, while
in others, it is the active site for a substrate transformation (references please). The most prevalent structural motif has
the Zn(II) in a tetrahedral coordination environment, ligated to the imidazole N in His, the thiolate S in Cys or to
carboxylate ligands of Asp or Glu. Research here focuses on the design of models for Zn-proteins and other
metalloproteins, where the ferrocene group is exploited as a structural scaffold that provides structural rigidity for
peptide residues and forces them into a conformation that is beneficial for metal coordination. Here we focus on the use
of His conjugates of ferrocene and the interaction of several ferrocenoyl histidine peptides was investigated with a
variety of divalent metal ions. Fc-peptide conjugates Fc[CO-His(Trt)-His(Trt)-OMe]2, Fc[CO-His(Trt)-Glu(OMe)OMe]2, and Fc[CO-His(Trt)-Glu(OMe)-OMe]2 were synthesized and observed to bind with metal ions Zn2+, Cd2+, Cu2+,
Ni2+, Mn2+, and Mg2+ in a 1:1 ratio. Interactions were monitored by 1H NMR spectroscopy and by ESI-TOF-MS.
1.
2.
3.
Rebilly, J.-N.; Colasson, B.; Bistri, O.; Over, D.; Reinaud, O. Chem. Soc. Rev. 2015, 44, 467-489.
Daniel, A. G,; Farrell, N.P. Metallomics, 2014, 6, 2230-2241.
Laitaoja, M.; Valjakka, J.; Jänis, J. Inorg. Chem. 2013, 52, 10983-10991.
P10
Old Dog, New Tricks: Developing the Coordination Chemistry of
2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT)
Jamie M. Frost, Amélie Pialat, Damir A. Safin, and Muralee Murugesu*
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada
jfrost@uottawa.ca; m.murugesu@uottawa.ca
Owing to the presence of three fused terpyridine-like coordination pockets, 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine
(TPymT, Figure 1 left) is a highly attractive ligand for the synthesis of discrete clusters, coordination polymers and
Metal-Organic Frameworks (MOFs). Despite its potential, the coordination chemistry of TPymT is vastly
underdeveloped – which can principally be attributed to the
hydrolysis of the central triazine fragment, which readily
occurs under mild conditions. Thus, after first being
synthesised in 1959 it had only been used a handful of
times to synthesise coordination compounds until our
group began reinvestigating its chemistry in 2013.[1] This
poster details our recent progress in developing the
coordination chemistry of TPymT, with a particular focus
on Ag+ (Figure 1 right) and Fe2+/Fe3+ chemistry.
Figure. 1 Molecular structure of TPymT (left) and a
[Ag9TPymT4]9+ segment (right).
See; E. I. Lerner and S. J. Lippard, J. Am. Chem. Soc., 1976, 98, 5397; E. I. Lerner and S. J. Lippard, Inorg.
Chem., 1977, 16, 1537 and A. M. Garcia, D. M. Bassani, J.-M. Lehn, G. Baum and D. Fenske, Chem. Eur. J.,
1999, 5, 1234.
39
P11
Initial Employment of 3-Hydroxy-2-naphthohydroxamic Acid
in Mn and Mn/Dy Cluster Chemistry
Dimosthenis P. Giannopoulos,1 Luis Cunha-Silva,2 George Christou,3 and Theocharis C. Stamatatos*,1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; REQUIMTE & Department of
3
Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal; Department of
Chemistry, University of Florida, Gainesville, Florida, USA
dg12eo@brocku.ca; tstamatatos@brocku.ca
The continuing interest in the synthesis and study of high-nuclearity transition
metal clusters in moderate-to-high oxidation states is driven by their
potentially interesting magnetic properties, including high-spin ground state
values (S) and single-molecule magnetism (SMM) behaviors.[1] Our group, and
others, has also had a longstanding interest in the synthesis of heterometallic
3d/4f SMMs, hoping that the co-presence of two different anisotropic and
high-spin metal ions within the same species will lead to SMMs with
unprecedented structural motifs, large energy barriers for the magnetization
reversal and blocking temperatures shifted to the liquid N 2 temperature
regime.[2] Towards this end, we turned our attention to the multidentate
chelating/bridging organic ligand 3-hydroxy-2-naphthohydroxamic acid
(nhaH2), a bulkier derivative of salicylhydroxamic acid, which has already
been successfully employed in 3d and 3d/4f metal cluster chemistry. [3] Herein,
we shall discuss our first results from the use of nhaH2 in Mn and Mn/Dy
cluster chemistry (Figure).
O
H
C
N
OH
OH
3-hydroxy-2-naphthohydroxamic acid (nhaH2)
Figure. (top) The ligand nhaH2, and (bottom) the
III
structure of a [Mn Dy ] cluster.
[1] G. Aromi and E. K. Brechin, Struct. Bonding (Berlin) 1997, 88, 1.
[2] Th. C. Stamatatos, S. J. Teat, W. Wernsdorfer and G. Christou, Angew. Chem. Int. Ed. 2009, 48, 521.
[3] M. R. Azar, T. T. Boron, J. C. Lutter, C. I. Daly, K. A. Zegalia, R. Nimthong, G. M. Ferrence, M. Zeller, J. W.
Kampf, V. L. Pecoraro and C. M. Zaleski, Inorg. Chem. 2014, 53, 1729.
P12
8
2
Rhenium and Ruthenium Complexes as Antibiotics Against Methicilin-Resistant
Staphylococcus Aureus (MRSA)
Anissa Brahami,a Baptiste Laramée-Milette,b Éric Déziel,a,* Garry Hananb,* and Annie Castonguaya*
a
b
INRS-Institut Armand-Frappier, Laval, QC, Canada; Université de Montréal, Montreal, QC, Canada.
anissa.brahami@iaf.inrs.ca; eric.deziel@iaf.inrs.ca, garry.hanan@umontreal.ca,
annie.castonguay@iaf.inrs.ca
Antibiotic resistance is a serious and growing phenomenon in contemporary medicine, and a primary public health
concern. Unfortunately, antibiotics are no longer the magic bullets that they once were. New resistance mechanisms
have emerged, making generations of antibiotics virtually ineffective, resulting in prolonged illness, greater risk of death
and higher costs. Thus, development of new antibiotics and other novel strategies are critically needed to overcome the
problems associated with antibiotic resistance. Transition metal complexes have unique properties, notably due to their
partially filled d-orbitals, and can lead to the discovery of antimicrobials that display novel modes of action and
interactions with biomolecules. In this presentation, preliminary results regarding the antibiotic activity of various
rhenium and ruthenium complexes bearing carbon monoxide and terpyridine-type ligands, against methicilin-resistant
Staphylococcus aureus (MRSA), will be reported.
40
P13
Reactivity of Neutral Ligands Toward the Alkylidene Moiety of Grubbs-type
Olefin Metathesis Catalysts
Faidh Hana, Timothy G. Larocque, Anna C. Badaj, and Gino G. Lavoie *
Department of Chemistry, York University, Toronto, ON, Canada
hfaidh@yorku.ca; glavoie@yorku.ca
Ruthenium alkylidene complexes are at the forefront of catalyst research due to the broad scope of possible olefin
metathesis transformations and substrates, including those with polar and protic functional groups. Studies of
decomposition pathways of these complexes are vital for designing catalysts with improved efficiency and lifetime.
Herein we discuss the sensitivity of the Ru=CHR active group to intramolecular insertions from “spectator” ligands. The
effect of the charge in ruthenium alkylidene complexes and the role of strong σ-donor weak π-acceptor phosphaalkenes
were investigated independently. Upon treatment of ruthenium alkylidene complex 1 with AgPF6, dicationic ruthenium
complex 2 was produced through nucleophilic attack from the N-heterocyclic carbene.1 Reaction of phosphaalkene 3
with RuCl2(PCy3)2(CHPh) produced complex 4, which also results from a migratory insertion of the phosphaalkene into
the benzylidene followed by two C-H activation.2 These findings provide important insights for designing the next
generation of ruthenium-based olefin metathesis catalysts.
(1) Larocque, T. G.; Badaj, A. C.; Lavoie, G. G. Dalton Trans. 2013, 42, 14955–14958.
(2) Larocque, T. G.; Lavoie, G. G. New J. Chem. 2014, 38, 499.
P14
Ring-Size Effects on Structures and Properties of Benzo-fused Dithiazolyl
Radicals
Mohamad Harb, Natalia Mroz, Yassine Beldjoudi, and Jeremy Rawson*
harbm@uwindsor.ca; jmrawson@uwindsor.ca
Sulfur-nitrogen free radicals have been developed in the design of both organic
magnets and conductors. This poster will examine the effects of increasing the ring
size (n = 1 – 3) on a series of benzo-fused dithiazolyls (1). The synthetic
methodology, structures and magnetic properties of these derivatives will be
discussed.
.
( )n
1
41
P15
Base Metal and Ruthenium Catalysts for the Synthesis of 1-butanol via the
Guerbet Reaction
Cassandra E. Hayes,1,2 R. Tom Baker,1* and William D. Jones2*
1
2
Department of Chemistry, University of Ottawa, Ottawa, ON, Canada; Department of Chemistry,
University of Rochester, Rochester, NY, USA
chayes8@ur.rochester.edu; rbaker@uottawa.ca; wjones@ur.rochester.edu
The development and widespread use of biofuels as replacements for traditional petrochemical fuels is an important and
growing issue to the global economy and environment. Current technologies cite ethanol as the most accessible
renewable fuel source; however, its use comes with a significant list of drawbacks. As such, ready access to so called
“advanced biofuels” (e.g. n-butanol) has become a topic of increasing interest to researchers. The homologation of
ethanol via the Guerbet process (figure) provides a renewable means of accessing n-butanol. Herein we demonstrate the
use of iron, cobalt, and ruthenium
dehydrogenation catalysts for their use
in the Guerbet process. Initial catalytic
studies show that iron and cobalt
catalysts catalyse the Guerbet reaction
with a high selectivity for the formation
of n-butanol over other longer chain byproducts.
P16
Synthesis and Characterization of Heteroleptic Copper(I) Complexes
for Light Harvesting Applications
Jennifer Huynh, Paloma Prieto, Jeanette A. Adjei, and Bryan D. Koivisto*
Department of Chemistry and Biology, Ryerson University, Toronto ON, Canada
jennifer3.huynh@ryerson.ca; bryan.koivisto@ryerson.ca
The dye sensitized solar cell (DSSC, or Grätzel cell) is a next generation photovoltaic device that shows remarkable
potential for solar energy markets. The powerhouse of the DSSC is the dye molecule, which has the ability to harvest
light, and convert it into electrical current. Inorganic dyes such as zinc porphyrins and ruthenium(II) complexes have
drawn much attention for their high efficiencies, but heteroleptic tetrahedral copper(I) complexes are a viable alternative
owing to their substantially lower cost and opportunity for development. The main challenge for using tetrahedral Cu(I)
dyes is their energetically favourable distortion to a square planar Cu(II) geometry upon oxidation. To prevent this,
phenanthroline-based ligands are particularly attractive due to their rigid bidentate structure, while functionalizing at the
2,9- positions on the phenanthroline ligand creates a steric environment preventing geometric distortion (Figure 1). This
presentation will focus on recent efforts towards the synthesis and characterization of novel ligands and heteroleptic
copper(I) complexes for light-harvesting applications.
Figure 1. Targeted motif of the Cu(I) complex dye molecule explored in this study.
42
P17
Inclusion Chemistry of 4-Phenyl-1,2,3,5-Dithiadiazolyl Radical in MIL-53(Al)
Erika M. Haskings and J.M. Rawson*
hasking@uwindsor.ca; jmrawson@uwindsor.ca
The interactions and applications of host-guest chemistry have generated considerable interest in recent years, with the
nature of the host···guest interaction leading to effects in which the host can modify the guest properties or reactivity or,
conversely, the guest affects the host structure. This poster will describe the inclusion chemistry of 4-phenyl-1,2,3,5dithiadiazolyl (PhDTDA) radical in the host metal-organic framework MIL-53(Al).
DTDA radicals tend to dimerise in the solid state but undergo monomer-dimer equilibria in solution. In this context we
have been interested to examine how the host affects the monomer-dimer equilibrium and chemical reactivity of the
radical. The PhDTDA radical was incorporated into the porous framework via gas phase diffusion and led to a colour
change of the host from white to red. Powder X-ray diffraction studies and DSC studies
revealed that the radical was included into the framework while solid state EPR studies
indicated low radical concentrations indicating a dimerization can occur within the host
cavities. The reactivity of the radical within the host-guest framework will be discussed.
Figure 1: 4-Phenyl-1,2,3,5-dithiadiazolyl (PhDTDA) radical
P18
Design and Synthesis of Lanthanide Single Molecule Magnets using the Schiff
Base Approach
Thomas Lacelle, Gabriel Brunet, Amélie Pialat, Rebecca J. Holmberg, Wolfgang Wernsdorfer, Ilia Korobkov, and
Muralee Murugesu*
tlace071@uottawa.ca; m.murugesu@uottawa.ca
Isostructural complexes of the formula [Ln4(H2htmp)4(MeOH)8](NO3)3(OH)·5MeOH·0.5H2O (Ln = GdIII 1, DyIII 2)
were synthesized using a new Schiff base ligand, abbreviated H 4htmp. Compound 2 exhibits ferromagnetic exchange
coupling under zero dc field with a large thermal relaxation barrier of Ueff = 158 K. To the best of our knowledge this
barrier is the sixth largest reported barrier for Schiff base complexes to date. The effect of the bridging tetrazine ring on
the magnetic exchange interactions is explored through structural and magnetic studies.
43
P19
Covalent Organic Frameworks: Using 2D Rigid Cores for Enhanced
Electron/Charge Transport
Andrew Hollingshead, François Magnan, and Jaclyn Brusso*
aholl097@uottawa.ca; jbrusso@uottawa.ca
Covalent Organic Frameworks (COFs) represent a relatively new class of crystalline porous materials that have emerged as
a novel strategy in the design of new functional materials. This may be attributed to their atomically precise integration of
building blocks into 2D or 3D topologies, which are characterised by lightweight elements, strong covalent bonds, high
specific surface area, defined pore size and great structural diversity. As a result, since the first reported COF in 2005, 1 a
great deal of research has focused on their development for use in a variety of applications such as catalysis, gas storage,
drug delivery, chemical sensing and organic electronics. In regards to the later, the designability of building blocks to
develop robust porous networks that feature 2D extended organic sheets
with
layered stacking structures in which periodic columnar π-arrays and
ordered 1D channels are generated is particularly attractive.
Our
approach to COFs involves the use of heteroaromatic building blocks
where the π-conjugation can be extended through various aromatic
“linkers” (e.g. benzene vs. naphthalene vs. anthracene). This extension
of πconjugation is anticipated to enhance the charge transport properties
while
creating a new family of semi-conductive materials. Preliminary work
towards the development of monomers 1 and 2, and their
implementation into COFs, will be presented.
1. Cote, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.; Matzger, A. J.; Yaghi, O. M., Science 2005, 310 (5751), 11661170.
P20
Reactivity of Iron Complexes of a Radical o-Phenylenediamine-based Ligand
Trevor Janes, Pavel Zatsepin, and Datong Song*
Department of Chemistry, University of Toronto, Toronto ON, Canada
tjanes@chem.utoronto.ca; dsong@chem.utoronto.ca
One of inorganic chemistry’s current goals is to exploit the ability of certain ligands to exist in multiple oxidation states.
Ideally, such ligands will work in concert with metals to accomplish challenging multielectron redox transformations. In
particular, o-phenylenediamine-derived ligands have received attention for their capability as
electron reservoirs.1 Our research group has investigated the coordination chemistry of a
sterically bulky o-phenylenediamide (L2-) towards Fe2+; we have observed its readiness to
oxidize into the o-diiminosemiquinonate (L-) form depicted in Figure 1.2 This poster
presentation will detail our application of the π-delocalized radical L- as a spectator ligand to
sponsor redox processes, facilitate N-group transfer, and stabilize three-coordinate iron.
Figure 1. Bulky o-diiminosemiquinonate (L-)
1. Broere, D. J., Plessius, R., van der Vlugt, J. I., Chem. Soc. Rev., 2015, 44, 6886-6915.
2. Janes, T., Rawson, J. M., Song, D., Dalton Trans., 2013, 42, 10640-10648.
44
P21
Asymmetric Hydrogenation by NHC-stabilized Borenium Ion Catalysis
Jolie Lam and Douglas W. Stephan*
jolie.lam@mail.utoronto.ca; dstephan@chem.utoronto.ca
Amines and their derivatives are synthetically
important compounds with a wide range of
applications, varying from dyes to pharmaceuticals.
In
particular,
potential
pharmaceutical
intermediates and targets are required in high
enantiopurity, which is typically achieved by chiral
transition metal-mediated transformations.1 Nheterocyclic carbene (NHC)-stabilized borenium
ions2 have recently been reported to be excellent
metal-free catalysts for the hydrogenation of
imines under mild conditions by Stephan and coworkers. We are now targeting the syntheses of new borenium ions that
incorporate chiral substituents for the enantioselective hydrogenation of prochiral imines. Borenium cations stabilized by
chiral bisoxazoline3 carbenes were synthesized and preliminary results show excellent catalysis with high conversions.
Simultaneously, we are tuning the Lewis acidity and selectivity of these systems by exploiting variations of the borane to
enhance reactivity.4 The efficacy of these systems in the asymmetric catalytic reduction of ketimines will be discussed.
1.
2.
3.
4.
Fleury-Brégeot, N.; Fuente, V.; Castillón, S.; Claver, C. ChemCatChem. 2010, 2, 1346-1371.
Farrell, J. M.; Hatnean, J. A.; Stephan, D. W.. J. Am. Chem. Soc. 2012, 134, 15728-15731.
Lindsay, D. M.; McArthur, D. Chem. Commun. 2010, 46, 2474-2476.
Farrell, J. M.; Posaratnananthan, R. T.; Stephan, D. W. Chem. Sci. 2015, 6, 2010-2015.
P22
1,1'-biphenyl-4,4'-diamonium bis[trifluoridostannate(II)]
(C10H12N2 2+, 2SnF3−)
G. Dénès1, *, A. Muntasar1 , T.N. Mouas2, S. Boufas2 and H. Merazig2
1
Laboratory of Solid State Chemistry and Mössbauer spectroscopy, Department of Chemistry and
2
Biochemistry, Concordia University, Montreal, QC, Canada; Laboratoire de Chimie Moléculaire, du
Contrôle de l'Environnement et de Mesures Physico-Chimiques, Département de Chimie, Faculté des
Sciences, Université des frères Mentouri de Constantine, Constantine, Algeria,
madenes@videotron.ca; hmerazig@gmail.com
Tin(II) organic-inorganic hybrid compounds are very rare. The only structural reports show that the compounds contain the
trifluorostannate(II) SnF3- ion. In the work presented here, the title compound was prepared upon reaction of SnF 2 and
benzidine in an H2O/HF solution at 80 oC. The crystal structure showed that, in contrast with the know fluorostannate(II)
hybrids, tin(II) is tetracoordinated. The electron pair geometry around tin is trigonal bipyramidal, while the molecular
geometry is see-saw, with the stereoactive tin lone pair being located on one of the equatorial positions, in agreement with
the VSEPR model of Gillespie and Nyholm. Each SnF4 unit is linked to two neighbors through bridging axial fluorine
atoms, to form infinite chains aligned parallel to one another to form corrugated sheets, with the tin lone pairs all pointing
perpendicularly to the tin sheets, forming sheets of lone pairs, resulting highly efficient cleavage planes. The large isomer
shift (δ = 3.016 mm/s) and quadrupole splitting (Δ = 1.825 mm/s) are expected for a tin(II) with a highly stereoactive lone
pair and bonded to fluorine.
45
P23
Nickel(Ⅱ) and Palladium(Ⅱ) Complexes of Perimidine-based Carbene Ligands:
Catalysis for C-N Coupling
Sojung Lee, T.-G. Ong, E. Perron, I. Korobkov, and Darrin Richeson*
slee228@uottawa.ca; darrin@uottawa.ca
The discovery of stable diaminocarbenes as well as their application as ligands for transition metals has had a tremendous
impact on the field of homogeneous catalysis. In this regard, we have designed novel perimidine-based diaminocarbenes as
ligands. These ligands have unique steric and electronic features. The Nickel (0), Nickel(Ⅱ) and Palladium(II) complexes
of these carbene ligands have been synthesized and details of their characterization will be presented. Our initial efforts to
exploit the unique properties of these carbenes and to reveal their potential in metal catalyzed transformations will be
described. For example, the Ni complexes have been found to have oxidative addition of aryl iodide and fluorinated
pydridine and the Pd complexes are active catalysts for C-N bond formation.
P24
Novel Methods of Preparations of Barium Tin(II) Fluorides by Leaching of
Chloride Fluorides in Water
G. Dénès1, *, A. Muntasar1 , and H. Merazig2
1
2
madenes@videotron.ca; muntsab@gmail.com
Preparations of BaSn2F6 and high performance fluoride conductor BaSnF4 were previously carried by precipitation from
aqueous solutions of tin(II) fluoride and barium nitrate for BaSn 2F6 and by high temperature reaction of SnF2 and BaF2
under inert atmosphere for BaSnF4. We have carried out an extensive study of barium tin(II) chloride fluorides. The
following compounds were prepared by precipitation between solutions of tin(II) fluoride and barium chloride: BaSn 2F6
(already known, new methods of preparation), BaSn2Cl2F4 (new), BaSnClF3.0.8H2O (new), and a very complex doubly
disordered Ba1-xSnxCl1+xF1-x solid solution (new). The same solid solution, with different properties and a much wider nonstoichiometry, was obtained by high temperature reactions between SnF2, BaF2 and BaCl2. In the course of the preparation
of the chloride fluorides, it was found that BaSn2F6 and BaSnF4 could be obtained by leaching the chloride fluorides. X-ray
diffraction 119Sn Mössbauer results will be presented.
46
P25
Thieno[3,2-b]thiophene-based Building Blocks for the Construction of 2D
Thienoacenes
François Magnan and Jaclyn Brusso*
fmagn030@uottawa.ca; jbrusso@uottawa.ca
Molecular electronics offer an enticing alternative to traditional silicon-based semiconductors, owing in large part to their
ease of fabrication and the associated lowered cost of production. Device stability and performance remain, however, major
limitations toward more generalized applications. And while charge mobility generally increases upon extension of the
conjugation, stability toward oxidation will usually decrease upon doing so. Incorporation of heteroatoms, such as sulphur,
in the polycyclic framework has been shown to be a viable strategy to address both of these issues. Concurrently, larger
orbitals on the heteroatoms promote π- π stacking and
efficient molecular overlap in the solid-state, a non-trivial
factor
in the performance of semiconductors. To this end, our
group
has focused on 2D thienoacenes (1, 2) as a way of
extending the effective conjugation, thus enhancing the
optoelectronic properties of the molecules. This
presentation will focus on current efforts toward the
integration of fused thiophenes systems as further ways
of
fine tuning the molecular properties.
P26
Friedel-Crafts Reactivity of a Highly Lewis Acidic Phosphonium Catalyst
Towards Benzyl Alcohols and Benzyl Ethers
James H. W. LaFortune, Jiantao Zhu, and Douglas W. Stephan*
james.lafortune@mail.utoronto.ca; dstephan@chem.utoronto.ca
The Fridel-Crafts reaction, wherein a Lewis or Brønsted acid catalyzes carbon-carbon bond formation, endures as the
preferred method of arene and heteroarene alkylation in many industries since its discovery in 1887. Over the past several
decades, significant efforts have been made to lower catalyst loadings and expand the substrate scope. While catalytic
Fridel-Crafts alkylations with benzylic alcohols are well known, alkylations with benzylic ethers are less common.
Furthermore, these reactions generally require high catalyst loadings of 5 to 10 mol%. 1 Recently, we have developed a new
class of Lewis acids based on highly electrophilic phosphonium cations. These species have been shown to be highly
reactive, facilitating these reactions with low catalyst loadings. 2 In this poster we explore the reaction of these Lewis acids
towards Friedel-Crafts alkylations with benzylic alcohols and ethers.
1 Reuping, M.; Nachtsheim, B. J.; Beilstein Journal of Organic Chemistry, 2010, 6, 6, doi:10.3762/bjoc.6.6.
2 Caputo, C. B.; Hounjet, L. J.; Dobrovetsky, R.; Stephan, D. W.; Science. 2013, 341, 1374. Pérez, M.; Hounjet, L. J.;
Caputo, C. B.; Dobrovetsky, R.; Stephan, D. W.; J. Am. Chem. Soc. 2013, 135, 18308.
47
P27
Stereochemical Reactivity of the Schiff Base Ligand
N-salicylidene-2-aminocyclohexanol in Lanthanide Chemistry
Eleni C. Mazarakioti,1 Katye M. Poole,2 Luís Cunha-Silva,3 George Christou,2 and Theocharis C. Stamatatos*1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada; Department of Chemistry,
3
University of Florida, Gainesville, Florida, USA; REQUIMTE & Department of Chemistry and
Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal
em12xb@brocku.ca; tstamatatos@brocku.ca
The employment of the cis-/trans-mixture of the Schiff base ligand
N-salicylidene-2-aminocyclohexanol, as well as its pure transanalogue, in lanthanide cluster chemistry has afforded complexes
with different nuclearities (Figure), indicating the stereochemical
effect of the ligand in the structural identity of polynuclear
compounds. Magnetic and optical studies revealed single-molecule
magnetism and photoluminescence behaviors for all the reported
compounds.1 The organic precursors of this work can be considered
as promising ligands for the construction of dual-acting molecular
species with potential applications in the field of molecule-based
electronics.
1
E. C. Mazarakioti, K. M. Poole, L. Cunha-Silva, G. Christou, Th.
C. Stamatatos, Dalton Trans., 2014, 43, 11456.
P28
Figure. The structure of one of the Ln8
clusters discussed in the present work.
Using the difference of Recoilless Fraction for Analytical Purposes
G. Dénès1, *, A. Muntasar1 , T.N. Mouas2, S. Boufas2 and H. Merazig2
1
2
madenes@videotron.ca;
The study of corrosion and surface oxidation of materials, and the protection mechanism, is a highly active area. Tin(II)
spectra can be used to contribute to this field. The energy of the 3/2 →1/2 γ-ray transition of 119Sn (23.8 keV) being
significantly lower than that of 57Fe (14.4 keV), the recoil-free fraction of tin compounds is lower than those of iron, at
equal lattice strength and at the same temperature. This gives weaker spectra, sometimes not detectable at ambient
conditions for weak lattices, such as SnCl2.2H2O, while they are easily detected at low temperatures when thermal
vibrations are frozen. In contrast, strong lattice rutile type SnO 2 has a very high recoil-free fraction and is easily detected at
room temperature, and the intensity of its line gains little from cooling. We have used the large recoil-free fraction of SnO2
to detect minor amounts of oxidation located in a very thin layer at the surface of particles of tin(II) compounds. We have
also used this method for probing the softness of Sn2+ stannous ion sites in comparison with more rigid Sn(II) covalently
bonded to fluorine, the two sites being randomly distributed in the doubly disordered Ba 1-xSnxCl1+yF1-y solid solution. The
large sensitivy of the recoil-free fraction to temperature changes also makes the tin-119 nuclide appropriate for the study of
lattice strength anisotropy (Goldanskii-Karyagin effect).
48
P29
Decomposition of Phosphine-Functionalized Metathesis Catalysts by Lewis
Donors: Generality and Implications
William L. McClennan, Justin A. M. Lummis, and Deryn E. Fogg*
bmccl098@uottawa.ca; deryn.fogg@uottawa.ca
Olefin metathesis is a powerful tool for the assembly of carbon-carbon double bonds. With industrial processes beginning to
emerge for the molecular metathesis catalysts, improved understanding of their decomposition pathways is becoming
increasingly important. We recently described “donor-induced decomposition” of the first-generation Grubbs catalyst
RuCl2(PCy3)2CHPh GI.2 Rapid degradation in the presence of pyridine occurred via a key σ-alkyl species which was
intercepted and characterized by NMR and X-ray analysis.1 Here we provide evidence that the second-generation Grubbs
methlyidene resting states GIIm follow a closely related pathway that is much faster than degradation of complexes in the
absence of pyridine. We also demonstrate that this pathway is general for Lewis donors with widely ranging basicity and
show the impact of this pathway during catalysis with various phosphine-functionalized Grubbs type catalysts. These
findings have important implications for the productivity of Grubbs-class metathesis catalysts.
(1) Lummiss, J. A. M.; McClennan, W. L.; McDonald, R.; Fogg, D. E. Organometallics 2014, 33, 6738-7741.
P30
Main Group Compounds Supported by an NHC Carbene Borate
Tho Nguyen and Georgii I Nikonov*
tho.nguyen@brocku.ca; gnikonov@brocku.ca
N-heterocyclic Carbene (NHC) ligands are ubiquitous in stabilising a variety of transition-metal complexes and find
numberless applications in catalysis. More recently, NHC ligands became popular also in main group chemistry and, in
particular, showed promise in the stabilization of low oxidation state main-group compounds.1-4 In this study, the anionic
NHC/borate ligand [(C6F5)3BCHC{N(2,6-Pri2C6H3)}2C:]-.Li+(THF)2 is employed for preparation of a series of main group
element compounds of Si, Ge, B and Zn. Furthermore, the latter can be converted into a Zn-hydride complex which is
being tested in catalytic hydrosilylation and hydroboration.
1. B. Kinjo, B. Donnadieu, M. A. Celik, G. Frenking, G. Bertrand, Science 2011, 333, 610.
2. K. C. Mondal, H. W. Roesky, M. C. Schwarzer, G. Frenking, B. Niepötter, H. Wolf, R. Herbst-Irmer, D. Stalke, Angew.
Chem., Int. Ed. 2013, 52, 2963.
3. Y. Li, K. C. Mondal, H. W. Roesky, H. Zhu, P. Stollberg, R. Herbst-Irmer, D. Stalke, D. M. Anrada, J. Am. Chem. Soc.
2013, 135, 12422.
4. Y. Xiong, S. Yao, S. Inoue, J.D. Epping, M. Driess, Angew. Chem., Int. Ed. 2013, 52, 7147.
49
P31
Tandem Catalysis for Water Splitting
Virginie Peneau, Nick Alderman, and Sandro Gambarotta*
peneau.virginie@gmail.com; sandro.gambarotta@uottawa.ca
Photocatalytic water splitting is a promising area for the production of hydrogen and oxygen. However, problems arise with
the separation of the mixture of gasses produced, adding large expenses to any commercialised systems. An attractive
proposal is to find a water splitting system involving a shuttle, such that the two gasses are released at separates points in the
cycle, negating the gas separation problem.
This study focuses on the separate production of oxygen and hydrogen from water splitting using tandem catalysis from
carriers that are able to be readily oxidised and reduced.
Two routes are considered; organic and inorganic carriers. Quinone/ benzoquinone is a bio-inspired organic carriers.
Quinone complexes are used by plants to store hydrogen and it has already been shown that quinone can be reduced and
oxidised using various catalyst or electrolysis. Inorganic carriers such as heteropolyacid complexes have shown promising
results using electrolysis. Silicotungstic acid complex was used as hydrogen and electron carrier from water splitting. In a
separate vessel hydrogen was released using platinum catalyst. 1
The combination of photoactive species such as TiO2 base catalyst, bismuth, vanadate, and cobalt able to reduce or oxidise
water with to these carriers is investigated.
Water oxidation mediated by a photosensitiser [Ru(bpy)3]2+ persulfate system is a known reaction using persulfate as a
sacrificial electron acceptor. The role of the carriers is to capture hydrogen and electrons. Another investigation is the use of
the previous carriers instead of persulfate with photosensitiser to allow the storage of hydrogen.
P32
Nickel(II) Clusters with Ferromagnetic and Emissive Properties from the Use
of a New Fluorescent Schiff Base Ligand
Panagiota S. Perlepe,1 Luís Cunha-Silva,2 Kevin Gagnon,3 Simon J. Teat,3 Albert Escuer,4 and Theocharis C.
Stamatatos*1
1
2
Department of Chemistry, Brock University, St. Catharines, ON, Canada, REQUIMTE & Department
3
of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal , Advanced
4
Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA, Departament de Quimica
Inorganica, Universitat de Barcelona, Barcelona, Spain
pp14kk@brocku.ca; tstamatatos@brocku.ca
The choice of the organic chelating/bridging ligand is currently one of the most
appealing chalenges towards the synthesis of new polynuclear 3d-metal complexes
with diverse physical properties, such as magnetism, optics, conductivity and catalysis.
In this work, we present the initial employment of the fluorescent bridging ligand Nnaphthalidene-2-amino-5-chlorobenzoic acid in Ni(II) cluster chemistry.1 Two new
Ni12 and Ni5 clusters with wheel-like and molecular-chain topologies, respectively,
were synthesized; the nature of the ligand has allowed unexpected transformations to
occur, as well as ferromagnetic and emission behaviors to emerge.
[1] P. S. Perlepe, L. Cunha-Silva, K. Gagnon, S. J. Teat, A. Escuer and Th. C.
Stamatatos, submitted to Chem. Eur. J.
Figure. Complete structure of the Ni12
wheel compound.
50
P33
A New Homogenous Tetradentate Ruthenium-Based Catalyst for the
Hydrodeoxygenation of Biomass-Derived Substrates in Aqueous Acidic Media
Konrad Piaseczny, Ryan Sullivanm and Marcel Schlaf*
kpiasecz@mail.uoguelph.ca; mschlaf@uoguelph.ca
Throughout the past century fossil fuels such as crude oil and natural gas have dominated the production of fuels and
petrochemicals. However, the use of these fossil-derived fuels has well-established negative environmental effects. A shift
to lignocellulosic biomass as a renewable carbon feedstock is therefore desirable, but also challenging as this carbon source
is characterized by an overfunctionalization with highly reactive hydroxyl and other oxygen groups. This problem can
however in principle be overcome through the use of catalytic hydrodeoxygenation reactions that reject oxygen as water.
This project focuses on the evaluation of trans-[Ru(2,9-di-(pyrid-2’-yl)-1,10-phenanthroline)(NCMe)2](OTf)2 as a
homogeneous, hydrogenation catalyst postulated to be stable at the required high temperatures (≥ 175 °C) due to
tetradentate chelation by the highly robust 2,9-di-(pyrid-2’-yl)-1,10-phenanthroline ligand. Complexation (see below) gives
the ruthenium complex, trans-[Ru(2,9-Di-(pyrid-2’-yl)-1,10-phenanthroline)(NCMe)2](OTf)2 in 86 % yield in high purity.
In preliminary test the catalysts realizes the
hydrogenation (175 °C, 800 psi H2, H2O) of 2,5hexandione, which forms part of a value chain
from cellulose to hexane, to 2,5-hexandiol and 2,5dimethylfuran in > 90 % yield without apparent
decomposition.
P34
Ru(II) and Ru(III)-Anastrozole Anticancer Drug Candidates
Golara Golbaghi, Mohammadmehdi Haghdoost, and Annie Castonguay*
INRS-Institut Armand-Frappier, Laval, Quebec, Canada
Golara.Golbaghi@iaf.inrs.ca; Annie.Castonguay@iaf.inrs.ca
Ruthenium complexes receiving increasing attention since antitumor agents NAMI-A and KP1019 successfully entered
phase II clinical trials. In comparison to various platinum compounds that are commonly used for cancer therapy, ruthenium
drug candidates are known to display a higher selectivity towards cancer cells, and to act via different modes of actions,
leading to fewer side effects and preventing the emergence of cancer cell resistance.
By combining cancer cell killing agents (ex: ruthenium) and cancer cell growth inhibitors (ex: Anastrozole), our research
aims at the discovery of superior anticancer therapeutics able to overcome the numerous problems associated with existing
chemotherapies. In this presentation, we will report the synthesis and the characterization of a variety of Ru(II) and Ru(III)Anastrozole complexes, as well as our preliminary results regarding their activity against human breast cancer cells.
51
P35
Toward the Development of New Energetic Ionic
Liquids as Green Hypergolic Fuels
Amélie Pialat,a Anguang Hu,b and Muralee Murugesu*,a
a
Department of Chemistry, University of Ottawa, Ottawa, ON,
b
Canada; Defense R&D Canada-Suffield Research Centre,
Medicine Hat, AB, Canada
apialat@uottawa.ca; m.murugesu@uottawa.ca
Rocket propulsion is due to the spontaneous ignition of hypergolic fuels
upon contact with oxidants inside a combustion chamber.1 This reaction
generates important volumes of hot gases creating thrust. Current
propellant systems mainly use hydrazine and its methylated derivatives as
hypergolic fuels however, they are highly volatile and carcinogenic. For
this reason, during the last decade, the unique properties of ionic liquids;
low vapour pressure, high thermal stability, low flammability and high
designability have considerably drawn attention in the research for new
green hypergolic fuels.2 In this poster, the design, synthesis and study of
the energetic properties of a new family of cyanoborohydride-based ionic
liquids will be presented.
[1] : Holtzmann, R. T. Chemical Rockets 1969, Marcel Dekker, New York.
[2] : Zhang, Q.; Shreeve, J. M. Chem. Rev. 2014, 114, 10527-10574.
P36
Metal Adamantyls; Synthesis and Reactivity
Kamalpreet Singh, Fioralba Taullaj, David Armstrong, and Ulrich W. Fekl*
Department of Chemistry, University of Toronto Mississauga, Mississauga, ON, Canada
kamalpreet.singh@mail.utoronto.ca; ulrich.fekl@mail.utoronto.ca
Since its discovery in 1933, adamantane has been at the forefront of
research in cage compounds.1,2 The diamondoid structure of
adamantane gives it unique properties for use in pharmaceuticals,
advanced materials, and catalysis. This versatility led to rigorous
investigation of the compound’s reactivity. The majority of the
chemical transformations affecting adamantane have been limited to
oxidations and halogenations, and very limited progress has been
in the synthesis of higher diamondoids.2,3 Our research aims to expand
scope of potential adamantane reactivity by developing novel metal
adamantyl complexes and exploring the subsequent reactivity of such
compounds. The synthesis and reactivities of a number of new
organometallic adamantyl complexes will be discussed.
1
made
the
based
Fort, R. C.; Schleyer, P. von R. Adamantane: Consequences of the Diamondoid Structure. Chem. Rev. 1964, 64 (3), 277.
V V Sevost’yanova and Mikhail M Krayushkin and A G Yurchenko. Advances in the Chemistry of Adamantane. Russian
Chemical Reviews 1970, 39 (10), 817.
3
Schwertfeger, H.; Fokin, A. A.; Schreiner, P. R. Angew. Chem. Int. Ed. 2008, 47, 1022-1036.
2
52
P37
A Homogeneous Ruthenium Catalyst Based on a Tetradentate Pyridine-Aniline
Ligand for the Hydrodeoxygenation of Biomass Derived Substrates to ValueAdded Chemicals in Aqueous Acidic Media
Maryanne Stones, Konrad Piaseczny, Ryan Sullivan, and Marcel Schlaf*
mstones@mail.uoguelph.ca; mschlaf@uoguelph.ca
The catalytic hydrodeoxygenation of biomass can
in
principle provide renewable carbon feedstocks
that
can replace or reduce the use of fossil carbon
sources in industrial applications. However, the
development of catalysts that are stable in
aqueous acidic media and at high temperatures,
and
exhibit promiscuous catalytic activity towards the
hydrodeoxygenation
of
biomass
derived
substrates is a currently unresolved challenge.
This
project focusses on the synthesis of a homogeneous catalyst based on a tetradentate nitrogen-donor ligand containing a rigid
benzene backbone and pendant pyridine groups. Following literature procedures, the ligand N,N'-Bis-(2-pyridylmethyl)-ophenylenediamine was synthesized in 40 % yield. A ruthenium complex intermediate [Ru(N,N'-Bis-(2-pyridylmethyl)-ophenylenediamine)(Cl)-(DMSO)](Cl) was prepared in 95 % yield. Metathesizing chloride for labile aceto- or benzo-nitrile
ligands with AgOTf at elevated temperatures, two potential catalysts were synthesized from this intermediate. Preparative
scale up of [Ru(N,N'-Bis-(2-pyridylmethyl)-o-phenylenediamine)(NCMe)2](OTf)2 required high-pressure and proved
difficult. The preparation of the alternative complex [Ru(N,N'-Bis-(2-pyridylmethyl)-o-phenylenediamine)(NCPh)2](OTf)2
at ambient pressure allowed structural characterization by mass spectrometry and NMR spectroscopy, but again preparation
on an experimentally and practically viable scale, as well as purification, is pending optimization of the preparative
protocol.
P38
Reactivity of Aryloxo Vanadium(III) and (IV) with Carbon Dioxide
Camilo Viasus, Nick Alderman, and Sandro Gambarotta*
cviasusp@uottawa.ca; sandro.gambarotta@uottawa.ca
Activation of small molecules like carbon dioxide by metal complexes is a great challenge due to the high thermodynamic
stability of CO2. If metal complexes are capable to afford deoxygenation or disproportionation, these transformations may
be attractive and useful as long as the process is catalytic. When a M-O function is formed as a by-product instead, the
reaction can be only stoichiometric. Nevertheless, when the transfer is limited to one electron, radical behavior might be
triggered. In this work we are modulating the one or two electron transfer using vanadium(III) and (IV) compounds. We
will present the possibility to switch from deoxygenation to radical behavior to form organic esters.
53
P39
Alkynyl-Based Fluorophosphonium Lewis Acids
Alexander Waked and Douglas W. Stephan*
alexander.waked@mail.utoronto.ca; dstephan@chem.utoronto.ca
Many industrial and pharmaceutical processes, such as hydrogenation and hydrosilylation, are catalyzed by transition metalbased systems. While these catalysts efficiently mediate these reactions, the dependence on precious metals, environmental
impact, and high cost have led to increased interest in developing metal-free alternatives. Previous research in the Stephan
group has shown that fluorophosphonium cations act as bulky Lewis acids and can catalyze hydrosilylation and
hydrodefluorination reactions. 1,2 The current study presents the synthesis of various alkynyl fluorophosphonium systems.
These species provide interesting avenues to the modification of the Lewis acidity at phosphorus and thus offer unique
approaches to new catalytic activity of fluorophosphonium compounds.
1. Caputo, C. B.; Hounjet, L. J.; Dobrovetsky, R.; Stephan, D. W., Science (Washington, DC, U. S.) 2013, 341 (6152), 13741377.
2. Holthausen, M. H.; Mehta, M.; Stephan, D. W., Angew. Chem., Int. Ed. 2014, 53 (25), 6538-6541.
P40
Enantiomerically Pure Bidentate Amine Tethered N-heterocyclic Carbenes:
Synthesis, Transition Metal Complexes and their Asymmetric Catalytic
Applications
Kai Y. Wan, Alan J. Lough, Heiko Rebmann, and Robert H. Morris*
kwan@chem.utoronto.ca; rmorris@chem.utoronto.ca
Certain precious metal complexes are efficient catalysts for the asymmetric hydrogenation (AH) of ketones and imines into
their corresponding enantiopure alcohols and amines, respectively. These products have wide industrial applications,
especially in the pharmaceutical industry. The AH catalysts, however, contain toxic and expensive metals and potentially
harmful and air-sensitive phosphorus ligands. As a consequence, the development of effective catalysts based on benign,
abundant metals such as iron1 and ligands based on organic compounds, such as NHC would provide a significantly greener
approach for AH.2,3 In this presentation, we will discuss our recent development of new chiral NHC ligands that bear
primary amine donors starting from chiral aminoalcohol precursors. This class is highly flexible due to handy electronic
modification at the NHC component and steric modification on the backbone and NHC substituents. Moreover, the amine
moiety can contain a third donor substituent that results in a highly rigid pincer-type ligand structure. During the talk, we
will focus on the coordination chemistry of this class of ligand on transition metals, especially iron. The second part of the
talk will be on the potential applications of this ligand in asymmetric hydrogenation.
1. Lagaditis P., Sues P., Sonnenberg J., Wan K., Lough A., Morris R., J. Am. Chem. Soc., 2014, 136, 1367–1380
2. O, W. W. N.; Lough, A. J.; Morris, R. H. Chem. Commun. 2010, 46, 8240.
3. O, W. W. N.; Morris, R. H. ACS Catal. 2012, 3, 32.
54
P41
Magnetic Circular Dichroism Studies of Iron-bound Human Calprotectin
Tessa M. Woodruff, Toshiki G. Nakashige, Elizabeth M. Nolan, and Michael L. Neidig*
Department of Chemistry, University of Rochester, Rochester, NY, USA
twoodru2@ur.rochester.edu; neidig@chem.rochester.edu
Magnetic Circular Dichroism
CP-Ser/Fe(II)
De (M -1 cm-1)
2.0
1.6
CP
1.2
0.8
0.4
0.0
DHis Asp-CP/Fe(II)
2.0
3
well
1.6
1.2
iron
-1
-1
De (M cm )
Calprotectin (CP) is a metal-sequestering protein found in large
quantities at sites of infection. It is believed that CP prevents
microbial infections by withholding the metal ions needed for
microbial replication and colonization. It has been shown that human
binds manganese, iron and zinc. From other studies, it has been
shown that CP also binds iron at its His4/His6 site, an unusual metal
binding site. Here, near-infrared magnetic circular dichroism (MCD)
studies are presented, which permit the evaluation of the coordination
number and geometry of iron(II)-bound CP and its comparison to
studied iron(II) metalloenzymes containing the common 2-His-1carboxylate facial triad iron-binding site. Both first coordination
sphere and distal site mutants are evaluated in order to further probe
binding in CP to confirm that iron(II) is bound in a distortedoctahedral geometry at the His4/His6 site.
0.8
0.4
0.0
6
8
10
12
3
14
16
-1
Energy (10 cm )
P42
Synthesis and Properties of BN-Heterocycles
Dengtao Yang and Suning Wang*
yang.dengtao@queensu.ca; suning.wang@chem.queensu.ca
Among π-conjugated organoboron compounds, BN imbedded aromatic molecules have attracted much research interest and
efforts.1The replacement of a C-C unit in an aromatic molecule with an isoelectronic B-N unit could lead to distinct changes
in its electronic, photophysical, and chemical properties. However, the syntheses of BN substituted polycyclic aromatic
hydrocarbons are in general very challenging.
In 2013, our group reported a photoelimination reaction involving BN-heterocycles.2 The elimination products are highly
luminescent and can be used as emitters in optoelectronic devices. Very recently we further investigated the elimination of
these kinds of BN-heterocycles via thermal pathways3 as well as in electroluminescent (EL) devices4.
(1) Campbell, P. G.; Marwitz, A. J. V.; Liu, S.-Y. Angew. Chem. Int. Ed.2012, 51, 6074.
(2) Lu, J. S.; Ko, S. B.; Walters, N. R.; Kang, Y.; Sauriol, F.; Wang, S. Angew. Chem. Int. Ed.2013, 52, 4544.
(3) Yang, D.-T.; Mellerup, S. K.; Wang, X.; Lu, J.-S.; Wang, S. Angew. Chem. Int. Ed.2015,54, 5498.
(4) Wang, S.; Yang, D.-T.; Lu, J.; Shimogawa, H.; Gong, S.; Wang, X.; Mellerup, S. K.; Wakamiya, A.; Chang, Y.-L.;
Yang, C.; Lu,Z.-H. Angew. Chem. Int. Ed.2015,DOI : 10.1002/anie.201507770.
55
P43
Converting Amines and Alcohols into Amides or Imines
Matthew Yosurack and Dmitry G. Gusev*
Department of Chemistry, Wilfrid Laurier University, Waterloo, ON, Canada
yosu5150@mylaurier.ca; dgoussev@wlu.ca
PNP and NNP osmium complexes from our laboratory[1,2]
catalize dehydrogenative coupling of alcohols and amines to
give imine and amide products, respectively, at 25 – 80 °C,
while using 0.05 – 0.2 mol% [Os].
[1] Bertoli, M.; Choualeb, A.; Lough, A. J.; Moore, B.;
Denis Spasyuk, D.; Gusev, D. G. Organometallics
2011, 30, 3479-3482.
[2] Spasyuk, D.; Vicent, C.; Gusev D. G. J. Am. Chem. Soc.
2015, 137, 3743-3746.
P44
Figure. Dehydrogenative coupling of primary
alcohols and amines.
Bone as a Target for Tungsten-Induced Toxicities: Answering Chemical Questions
about Tungsten Deposition in Bone to Elucidate Toxicological Mechanisms
Cassidy VanderSchee and Scott Bohle*
cassidy.vanderschee@mail.mcgill.ca; scott.bohle@mcgill.ca
Though tungsten is increasingly used in industrial, commercial and medical applications, very little is known regarding its
toxicity at high concentrations largely due to a persisting and unfounded belief in this metal’s inert nature. This gap in
knowledge has recently been highlighted by several cases where high level exposure to tungsten was correlated to severe
medical issues such as leukemia, stroke and seizures. Tungsten has been shown to accumulate in bone with preliminary
studies suggesting that there may be detrimental effects on both bone structure and the immune cells produced in bone
marrow. Through a combination of X-ray Absorption Spectroscopy (XAS) techniques and the use of novel fluorescent
tungsten chelators, we intend to determine tungsten localization and speciation within bone tissue. Establishing the nature
of tungsten in bone will reveal how tungsten deposition affects bone’s structural integrity and gives rise to observed
toxicity.
56
P45
Water-soluble Platform for Selective Fe(II), Fe(III), Ru(III) and Zn(II) Detection
Nadia O. Laschuk and Olena V. Zenkina*
Faculty of Science, University of Ontario Institute of Technology, Oshawa, ON, Canada
Olena.Zenkina@uoit.ca
Transition metals play a vital role in biology and chemistry. Being the most abundant essential trace element in the
human body, iron participates in crucial physiological processes such as oxygen transport, electron transfer, and
enzymatic catalysis. Zinc is the second most abundant transition metal in human body after iron. Unlike iron,
which is required for certain specific functions, zinc is required for general metabolism. However, increased
dietary iron and zinc may cause Alzheimer’s disease, and is linked to development of cancer. 1 Even though
ruthenium is not an essential trace element in the human body, it may have significant impact on human health; in
particular, ruthenium complexes were shown to form cross-links with nucleic acids to halt DNA replication. 2
Although significant progress has been made in monitoring of Fe(II), Fe(III), Zn(II) and Ru(III) as single-analyte
ions, as well as in detection of Fe(II)-Fe(III) pair, recent research efforts have been focused on the development of
assays that allow simultaneous multi-analyte detection, which is especially important in environmental testings,
food chemistry and molecular biology. 3
We report on development of a thoroughly water soluble platform for rapid and sensitive (ppb to ppm lev el)
detection of Fe2+, Fe3+, Ru3+, and Zn2+ in multicomponent aqueous solutions. Upon reaction with abovementioned
metal ions, it produces a non-distractive Uv-vis and fluorescence readouts that can be analyzed and interpreted
using logic gates concept. Use of the platform do not require preliminary sample treatment, resulting in successful
metal ions discrimination in situ and thus can be potentially applicable for analysis of environmental, food,
biological and biomedical aqueous systems.
1. (a) C. P. Wen, et al Cancer Res., 2014, 74, 6589-6597; (b) L. C. Costello and R. B. Franklin, Mol. Cancer, 2006,
5, 17.
2. A. Bergamo, et al. J. Inorg. Biochem., 2012, 106, 90-99
3. Z. Zhang, D.S. Kim, C.-Y. Lin, H. Zhang, A.D. Lammer, V. M. Lynch,I. Popov, O. Š.Miljanić, E. V. Anslyn, J. L.
Sessler, J. Am. Chem. Soc. 2015, 137, 7769-7774.
P46
An Organo-Thulium Family of Single-Ion Magnets: Is Symmetry Enough?
Katie L. M. Harriman, Ilia Korobkov, and Muralee Murugesu*
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, Canada
kharr093@uottawa.ca; m.murugesu@uottawa.ca
Single-molecule magnets (SMMs) exhibit slow relaxation of the magnetization of purely molecular origin, making them
excellent candidates for electronics-based applications; specifically in high-density information storage, molecular
spintronics, and quantum computing. However, implementation of these types of materials into practical devices will rely
heavily on increasing their energy barrier to spin reversal (Ueff). Throughout the last decade, growing research efforts have
been directed towards the synthesis of single-ion magnets (SIMs) with the goal of maximizing Ueff through tailoring singleion anisotropy. The 4f-elements represent excellent candidates for SIMs due to their large intrinsic magnetic anisotropy,
however, they are often plagued with significant ground state quantum tunneling of the magnetization (QTM), which
drastically reduces Ueff.. This problem becomes even more difficult to overcome in non-Kramers ions, (integer spin systems)
where ground state QTM is not formally forbidden as it is with Kramers ions (non-integer spin systems). One of the ways to
circumvent this problem is to design systems which exhibit very high symmetry. As such, we have turned our attention
towards organometallic compounds; where we have synthesized a family of cyclooctatetraenide (COT 2-) complexes with
thulium, a non-Kramers ion (S = 1). Thulium remains one of the most rarely studied lanthanide ions, both in terms of its
chemistry and its slow relaxation properties. This presentation will outline the synthetic route, and the subsequent
challenges faced in designing a family of organo-thulium complexes, as well as their SIM properties investigated through
SQUID magnetometry.
57
P47
Arsenic Speciation in Mushrooms Subject to Thermal Treatments
Jessica Henry, Iris Koch,* Jennifer Scott,* and Kenneth J. Reimer*
Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, ON,
Canada
jessica.henry@rmc.ca; koch-i@rmc.ca; jennifer.scott@rmc.ca; reimer-k@rmc.ca
Arsenic is an element found in the environment in many different chemical forms (referred to as species), each having
unique chemical, physical and biological properties. The different species range in their toxicities, with among the most
toxic arsenic species including inorganic forms, such as arsenite (As(III)) and arsenate (As(V)). Generally, pentavalent
organoarsenic compounds are less toxic and aresenobetaine (AB) is the only species considered non-toxic. Where there are
no natural or anthropogenic sources of arsenic contamination, food is the main source of intake for this metalloid. Higher
levels of arsenic are generally found in foods such as seafood, rice, and sometimes mushroom. AB is the principal arsenic
form in seafood and many mushrooms species. Preparations of food, such as cooking treatments, have been found to alter
the arsenic speciation in seafood such as the degradation of AB to dimethylarsinic acid (DMA), and tetramethylarsonium
ion (TETRA), as well as less prevalent amounts of arsenocholine (AC) and monomethylarsonic acid (MMA). In this study,
four edible mushroom species (Lactarius deliciosus, Leccinum scabrum, Boletus edulis and Calvatia gigantea) were
collected and treated to simulate cooking scenarios (barbequed and fried). The samples were analyzed for total arsenic using
ICP-MS and for arsenic species using HPLC-ICP-MS. A consistent decrease in the total arsenic concentration was seen in
all of the cooked samples, in comparison to their raw (untreated) concentrations. AB was found to be transformed to more
toxic forms in both the fried and barbequed samples for the Calvatia sp.. Therefore, it may be necessary to consider the
effect of thermal treatments on arsenical species when determining risk associated with mushroom intake.
P48
Benzimidazolium Bicarbonates as Air-stable Precursors of N-Heterocyclic
Carbenes (NHCs): Novel Synthetic Routes and Applications to Gold Surfaces
Mina R. Narouz, Christene A. Smith, Cathleen M. Crudden,* and J. Hugh Horton*
13mn23@queensu.ca; cruddenc@chem.queensu.ca; hugh.horton@chem.queensu.ca
Recent results from the Crudden and Horton laboratories demonstrated the formation of ultrastable self-assembled
monolayers (SAMs) of N-heterocyclic carbenes (NHC) on gold surfaces where NHCs were generated in a glove box
using a strong base.1 Although Fèvre et al. showed that imidazol(in)ium bicarbonates could behave as an air stable source
of NHCs, their procedures for the preparation of imidazolium bicarbonates via anion-metathesis using KHCO3 resulted in
highly variable levels of exchange.2 In our current work, novel synthetic routes were developed to prepare pure, air-stable
benzimidazolium bicarbonates ([NHC(H)][HCO3] ) from the iodide counterparts. For the first time, these bench-stable
bicarbonates were shown to effectively form NHC-based SAMs on gold surfaces in methanol at room temperature
without the need for water and oxygen-free conditions.
1
Crudden
M. et al., Nature Chem., 2014, 6, 409-414.
2
Fèvre M. et al., J. Am.Chem. Soc., 2012, 134, 6776–6784.
58
C.
P49
Picolyl-NHC Metal Complexes: Syntheses and Reactivities
Qiuming Liang, Trevor Janes and Datong Song*
walter.liang@mail.utoronto.ca; dsong@chem.utoronto.ca
The chemistry of metal-ligand cooperation is useful in many bond activation processes. Milstein has demonstrated a mode
of H-Y (Y = H, OH, OR, NH2, NR2, C) bond activation via aromatization-dearomatization processes in pyridine- or
acridine- based tridentate (PNN or PNP) pincers1. This system is successfully used as catalysts in many environmentally
benign transformations with different metal centers1. Our group has studied similar pincer on ruthenium by substituting the
phosphours arm by NHC2. We are then interested in related bidentate cooperative ligands on earth abundant metals (ie. Iron,
cobalt, nickel). Picolyl-NHC type ligands are chosen to study as it contains pyridyl methylene which should be accessible
towards aromatization- dearomatization and further bond activations (Scheme 1.). By coordination to iron and
deptrotonation, low coordinate iron chemistry can also be explored. This poster illustrates picolyl-NHC iron(II) complexes
syntheses. Preliminary results of reactivities and deprotonation study are also presented.
Scheme 1. Proposed aromatization-dearomatization on picolyl-NHC iron system.
1. D. Milstein et al., Acc. Chem. Commun. 2011, 588
2. D. Song et al., Chem. Commun. 2011, 8349
59
Participants
ACS International – CAS
Dr. Mostafa Hatam
Pine Research Instrumentation
Dr. Li Sun
Air Liquide Canada Inc.
Ross Stirling
Matt Coleman
Queen’s University
Prof. Cathleen Crudden
Dr. Matthew Zamora
Dr. Patrick Eisenberger
Mohammed Affan
Zach Ariki
Edward Cieplechowicz
Joshua Clarke
Ramjee Kandel
Shuang Liang
Sean McDonald
Colleen McIlwain
Jennifer McLeod
Soren Mellerup
Mina Narouz
Sarah Piotrkowski
Jason Rygus
Dengtao Yang
Brock University
Prof. Georgii Nikonov
Prof. Theocharis Stamatatos
Prof. Melanie Pilkington
Prof. Costa Metallinos
Iryna Alshakova
Tho Nguyen
Dimitrios Alexandropoulos
Panagiota Perlepe
Alysha Alaimo
Eleni Mazarakioti
Paul Richardson
Dimosthenis Giannopoulos
Marnie Edwardson
Majeda Al Hareri
Bruker
Dr. Dan Frankel
Cary Bauer
Joseph Weiss
Concordia University
Prof. Xavier Ottenwaelder
Prof. Georges Denes
Dr. Abdualhafed Muntasar
Laura Andrea Rodriguez Solano
INRS - Université du Québec
Prof. Annie Castonguay
Dr. Medhi Haghdoost
Anissa Brahami
Golara Golbaghi
Amal Thamri
McGill University
Dr. Kristopher Rasadiuk
Dr. Munendra Yadav
Cassidy Vanderschee
McMaster University
Prof. David Emslie
Jeffrey Price
MEGS Specialty Gases Inc.
David de Bellefeuille
Rigaku Oxford Diffraction
Dr. Lee Daniels
Prof. Ken J. Reimer
Prof. Gord Simons
Prof. Danny Pagé
Prof. Jennifer Scott
Capt. Ross Franklin
Capt. Nicholas Beaudry
Capt. Matt McTaggart
Capt. Craig Williams
Vishva Shah
Jessica Henry
Ryerson University
Prof. Daniel Foucher
Dr. Aman Khan
Jasveer Dhindsa
Jennifer Huynh
Julie Loungxay
Jeffrey Pau
Muhammad Yousaf
Systems for Research
Jerry Windsor-Martin
Université de Montréal
Prof. Frank Schaper
Prof. Davit Zargarian
Thomas Auvray
Suéli Bonafim
Pargol Daneshmand
Antoine Douchez
Valérie Hardouin Duparc
University of Guelph
Prof. Marcel Schlaf
Elnaz Latifi
Konrad Piaseczny
Maryanne Stones
University of Ontario Institute of
Technology
Prof. Olena Zenkina
University of Ottawa
Prof. Muralee Murugesu
Prof. Jaclyn Brusso
Prof. Tom Baker
Prof. Deryn Fogg
Dr. Jamie Frost
Dr. Cassandra Hayes
Nicholas Alderman
Gwendolyn Bailey
Adrian Botti
Alex Daniels
Emily Gee
Katie Harriman
Andrew Hollingshead
Rebecca Holmberg
Elizabeth Kleisath
Thomas Lacelle
Sojung Lee
Maykon Lemes
François Magnan
William McClennan
Virginie Peneau
Stephanie Rufh
Ryan Sullivan
Camilo Viasus
Nathan Yutronkie
Yixin Zhang
University of Pennsylvania
Prof. Daniel J. Mindiola
Université des frères Mentouri de
Constantine, Algeria
Prof. Hocine Merazig
60
University of Rochester
Prof. Michael Neidig
Stephanie Carpenter
Tessa Woodruff
University of Toronto
Prof. Robert Morris
Prof. Ulrich Fekl
Maryam Abdinejad
Julia Bayne
Karl Demmans
Louie Fan
Trevor Janes
James LaFortune
Jolie Lam
Kamalpreet Singh
Samantha Smith
Fioralba Taullaj
Alexander Waked
Kai Wan
Pavel Zatsepin
University of Toronto Scarborough
Dr. Zhe She
Dr. Iraklii
Annaleizle Ferranco
University of Windsor
Prof. Jeremy Rawson
Justin Binder
Mohamad Harb
Erika Haskings
Mitchell Nascimento
Western University
Prof. Johanna Blacquiere
Dr. Patrick Crewdson
Ryan Maar
Samantha Novoa
Wilfred Laurier University
Prof. Dmitri Goussev
Prof. Oleg Shirobokov
Matthew Yosurack
York University
Prof. Barry Lever
Prof. Lavoie
Faidh Hana
Nick Zinck
Conference Chair
Jennifer Scott
Assistant Chair
Capt. Ross Franklin
Organizing Committee
Vishva Shah
Rick Melanson
Capt. Nicholas Beaudry
Website and Finances
Bryan Bailey
Mary Darlington
Special Mention
RMC Club of Canada
Department of Chemistry and Chemical Engineering
Thank you to all of our volunteers !!
Matt McTaggart
Jennifer Snelgrove
Neda Bavarian
Michelle Nearing
Deborah Durbin
Summer Li
Diana Tyner
Laura Oligvie
Shuang Liang
Anbareen Farooq
Jessica Henry
Emily Corcoran
Nicholas Bourgon
Zackary Thomson
Tristan Blaikie
Eliot Sulima
Melanie Hughes
Kela Weber
Marc Button
Kommy Farahani
Brandon Kiedyk
William Payton-Stewart
Jonathan Saulnier
Olivier Lebel
Alex Beaulieu
Myrian Rochon
Victoria Brown
Trevor Reid
Andrew Juvonen
Michael Skipwith
Clarize Virtusio
Jaden Rook
Tae Kim
Jacob Tamman
Kieran Marks
Gabriel Paquet
Ian Marcoux
Paul Chan
Pavel Samuleev
Daniela Loock
61
Capt. Brent Limbeek
2Lt. Rabia Soni
Samantha McDermott
William Carle
Alex Landry
Capt. Craig Williams
Hugo Hazledine
Mitchell Brown
Michael Cherry
Varun Senthilkumar
Blaire Coffey
Kevin Pathinather
Morgan Chaffee-Goehr
Jordon Gjelsvik
Gregory Garber
Cecily McDonnell
Linda Marois
Kathy Nielsen
Tim Nash
John Saunders

IDW48-2015 See Program - inorganic discussion weekend

Transcription

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