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RESEARCH

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Developing the Coordination Chemistry of Heavy Main Group Metals

The overall goal of our research is the development of the coordination chemistry of heavy main group metals (e.g. In, Bi), which possess interesting and useful Lewis acid properties. We achieve this through the synthesis and characterization of series of organometallic compounds which systematically alter the metal bonding environment and ability to facilitate chemical reactions.

 

Areas of focus include:

Reactive Main Group Metal Compounds via Redox-Active Ligands

A focus of contemporary main group chemistry is the design of alternatives to expensive and toxic transition and rare earth metal organometallic catalysts for organic transformations important to the fine chemicals and pharmaceuticals industries. Precious metals favour two-electron redox changes and are well-suited for “oxidative addition” and “reductive elimination” processes required for organic coupling reactions. However, high costs and environmental concerns associated with the toxicity of these metals and the search for new reactivity profiles has led to exploration of more environmentally friendly and inexpensive main group metals. Indium(III) and bismuth(III) reagents are well-established Lewis acid catalysts in organic syntheses and meet these criteria. However, their use for oxidation/reduction reactions is much less developed as both metals are predominantly stable in their 3+ oxidation states and do not readily undergo reversible oxidation reactions. An alternative route to designing main group metal compounds capable of redox reaction chemistry is therefore through use of redox-active ligands. We are preparing indium and bismuth compounds using anionic ligands such as ferrocenyl, o-amidophenolates and catecholates that are are capable of reversible one-electron oxidation. The electrochemical and photochemical properties of these novel compounds are being determined, and they are being screened for their reactivity with oxidants, reductants and substrates to assess their potential as redox catalysts.   Ultimately, this research may lead to new classes of homogeneous organometallic catalysts that possess unique reactivity and afford novel chemical products.

Catalysts for the Production of Green Materials and Biofuels

Lewis acidic indium(III) compounds have gained significant attention as catalysts for the ring opening polymerization (ROP) of lactones, due to their new reactivity profile and relatively low toxicity versus aluminum and tin-based catalysts. We are preparing organoindium bisthiolate compounds that incorporate multiifunctional thiolate ligands. The thiolate functionality anchors the ligand to the indium centre via a strong hydrolytically stable covalent bond, while amine, ether, or thioether functionalities fill coordination sites and prevent the formation of coordination polymers via extensive intermolecular In…S bonding. We are also developing analogous bismuth compounds, as well as water-stable indium and bismuth thiolates which are being screened for their ability to catalyze various organic reactions in aqueous media, such as those important to the production of biofuels. 
 

‘Synthesis, Electrochemistry, and Reactivity of Bismuth(III) and Indium(III) Dithiolene Complexes” Heidi Atto, Glen G. Briand, Tanner George, Viveka K. Kulkarni, John. S. Lee, Jason D. Masuda, Brian J. MacLean, Jennifer A. Melanson, Gregory M. Sandala, Padmapriya Srinivasan and Lauren J. Wentzell. Canadian Journal of Chemistry, 2025, dx.doi.org/10.1139/cjc-2024-0249. (Invited Article, Special Issue in Memory of Professor Steve Westcott). Abstract

‘Redox-Active Ligands – a Viable Route to Reactive Main Group Metal Compounds’ Glen G. Briand. Dalton Transactions, 2023, 52, 17666-17678. (Invited Frontier Review Article) Full Text

 

‘Synthesis, Structure and Reactivity of Organoindium 1,2-Benzenedithiolates and 2-Amidobenzenethiolates’ Glen G. Briand, Tanner George, Gregory A. MacNeil, Jason D. Masuda, Brian J. MacLean, Michael W.R. Mosher, Gregory M. Sandala, Padmapriya Srinivasan, Alexander H. Stockli, Rachel L. Vanderkloet and Charles J. Walsby. European Journal of Inorganic Chemistry, 2022, e202200542 (16 pages). Full Text

‘Synthesis and Structural Characterization of Methylindium Imino/Aminophenolates: Comparison to Aluminum Analogues and Reactivity Toward the Coupling Reactions of Carbon Dioxide with Epoxides’ Kori A. Andrea, Adam R. Beckett, Glen G. Briand, Sarah A. Martell, Jason Masuda, Kathleen M. Morrison and Emilie M.T. Yammine. Journal of Organometallic Chemistry, 2020, 919, 121307.  Abstract  

‘Synthesis, Structural Characterization, and Reactivity of (Thiolato)bismuth Complexes as Potential Water-Tolerant Lewis Acid Catalysts’ Glen G. Briand, Andreas Decken, Whitney E.M.M. Shannon and Eric E. Trevors. Canadian Journal of Chemistry, 2018, 96, 561-569. (Invited Article, Special Issue to Honour Professor Neil Burford)  Abstract

 

‘Synthesis, Structural Characterization and Reactivity of (Dithiolato)indium Complexes' Timothy S. Anderson, Glen G. Briand, Ralf Bruening, Andreas Decken, Matthew J. Margeson, Heidi M. Pickard and Eric E. Trevors. Polyhedron, 2017, 135, 101-108.  Abstract

 

Synthesis and Crystal Structure of Bis(μ-2-methylbenzenethiolato-κ2S:S)bis[methyl(2-methylbenzenethiolato-κS)indium(III)]’ Glen G. Briand, Andreas Decken, Courtney M. Dickie and Gregory MacNeil. Acta Crystallographica, 2017, E73, 481-483. Full Text

 

‘Strained Metal Bonding Environments in Methylindium Dithiolates and Their Reactivity as Initiators for the Ring-Opening Polymerization of Cyclic Esters’ Glen G. Briand, Stefan A. Cairns, Andreas Decken, Courtney M. Dickie, Thomas I. Kostelnik and Michael P. Shaver. Journal of Organometallic Chemistry, 2016, 806, 22-32. Abstract

 

‘Synthesis and Structural Characterization of Cyclic Indium Thiolate Complexes and Their Utility as Initiators for the Ring-Opening Polymerization of Cyclic Esters’ Laura E.N. Allan, Glen G. Briand, Andreas Decken, Jessica D. Marks, Michael P. Shaver and Ryan G. Wareham. Journal of Organometallic Chemistry, 2013, 736, 55-62. Abstract

Coordination Complexes of Heavy p-Block Metal Thiolates

We have prepared coordination complexes of heavy p-block metal thiolate compounds with a variety of Lewis base donor ligands. By altering the thiolate and Lewis base donor ligand, we have been able to isolate a variety of new bonding environments for Pb (II) and interesting extended solid-state structures. Further, we have been able rationalize the metal coordination geometries using DFT and solid-state NMR spectroscopy.

‘Structural Variation in Ethylenediamine and -Diphosphine Adducts of (2,6-Me2C6H3S)2Pb: A Single Crystal X-ray Diffraction and 207Pb Solid- State NMR Spectroscopy Study’ Aaron J. Rossini, Alan W. Macgregor, Anita S. Smith, Gabriele Schatte, Robert W. Schurko and Glen G. Briand. Dalton Transactions, 2013, 42, 9533-9546. Abstract

‘Structure and Reactivity of the Cationic Lead(II) Thiolate [(4-Me3NC6H4S)6Pb3][PF6]6’ Glen G. Briand, Andreas Decken, Mathew C. Finniss, April D. Gordon, Naomi E. Hughes, and Lauren M. Scott. Polyhedron, 2012, 33, 171-178. Abstract

‘Bis(pentafluorobenzenethiolato)bis(pyridine)lead(II)’ Sarah E. Appleton, Glen G. Briand, Andreas Decken and Anita S. Smith. Acta Crystallographica, 2011, E67, m714. Full Text

'Probing Lead(II) Bonding Environments in 4-Substituted Pyridine Adducts of (2,6-Me2C6H3S)2Pb: An X-ray Structural and Solid-State 207Pb NMR Study' Glen G. Briand, Andrew D. Smith, Gabriele Schatte, Aaron J. Rossini and Robert W. Schurko. Inorganic Chemistry, 2007, 46, 8625-8637. Abstract

‘Monomeric, One- and Two-dimensional Networks Incorporating (2,6-Me2C6H3S)2Pb Building Blocks’ Sarah E. Appleton, Glen G. Briand, Andreas Decken and Anita S. Smith. Journal of the Chemical Society, Dalton Transactions, 2004, 3515-3520. Abstract

 

 


Precursors for Binary Inorganic Semiconductor Materials

We have prepared the physical properties of organometallic compounds containing group 13-15 and group 13-16 element bonds. These may be potential high-purity organometallic 'single-source' precursors for the thin-film methods employed in the preparation of semiconductor materials (e.g. MOCVD).

 

‘Crystal structure of dimethyl-1κ2C-bis(μ-4-methylphenolato-1:2κ2O:O)(N,N,N’,N’-tetramethylethylenediamine-2κ2N,N’)indium(III)lithium(I)’ Glen G. Briand, Andreas Decken and Marshall R. Hoey. Acta Crystallographica, 2015, E71, m257-258. Full Text

 

‘catena -Poly[bis[dimethyl(pyridine-κN)indium(III)]-μ4-benzene-1,3-diolato-bis[dimethyl-lindium(III)]-μ4-benzene-1,3-diolato]’ Glen G. Briand, Andreas Decken and Marshall R. Hoey. Acta Crystallographica, 2013, E69, m622. Full Text

 

'Investigating Intermolecular Bonding in Diphenylbismuth(III) Chalcogenolates: X-ray Crystal Structures of (Ph2BiSR’) (R’ = Ph; 2,6-Me2C6H3)' Glen G. Briand, Andreas Decken, Nicole M. Hunter, Graham M. Lee, Jennifer A. Melanson and Evan M. Owen. Polyhedron, 2012, 31, 796-800. Abstract

‘A Structural Investigation of Dimethylthallium(III) Thiolate and Selenolate Rings and Polymers’ Glen G. Briand, Andreas Decken, Nicole M. Hunter, John A. Wright and Y. Zhou. European Journal of Inorganic Chemistry, 2011, 5430-5436. Abstract

‘Bis(μ-diethylphosphido-κ2P:P)bis[bis(2,4,6-trimethylphenyl)indium(III)]’ Glen G. Briand, Andreas Decken, Dane A. Knackstedt and Caleb D. Martin. Acta Crystallographica, 2011, E67, m1578. Full Text

‘Structural Effects of Varied Steric Bulk in 2,(4),6-Substituted Dimethylthallium(III) Phenoxides’ Glen G. Briand, Andreas Decken, J. Ian McKelvey and Yukun Zhou. European Journal of Inorganic Chemistry, 2011, 2298-2305. Abstract

'Rationalizing Oligomerization in Dimethylindium(III) Chalcogenolates (Me2InER’) (E = O, S, Se): A Structural and Computational Study'. Glen G. Briand, Andreas Decken and Nathan S. Hamilton. Dalton Transactions, 2010, 39, 3833-3841. Abstract

‘Substituent Effects on Indium-Phosphorus Bonding in (4-RC6H4S)3In-PR’3 Adducts (R = H, Me, F; R’ = Et, Cy, Ph): A spectroscopic, Structural and Thermal Decomposition Study’. Glen G. Briand, Reagan J. Davidson and Andreas Decken. Inorganic Chemistry, 2005, 44, 9914-9920. Abstract

Models for Indium Radiopharmaceuticals

The radionuclide indium-111 is currently being employed in 'radiopharmaceuticals' for diagnostic medical imaging. Introduction of this element into biological systems requires the formation of complexes with specific in vivo behavior. Our studies of the coordination chemistry of indium involves preparing ligands that afford complexes with high kinetic stability. Further, the interaction of the resulting metal-ligand complexes with biologically relevant molecules is being examined.

'Bis-imine Primary Amine Protection of the Dialkyltriamine, Norspermidine' Adrian S. Culf, Jennifer A. Melanson, Rodney J. Oulette and Glen G. Briand. Tetrahedron Letters, 2012, 53, 3301-3304. Abstract

'A Preferred Bonding Motif for Indium-Aminoethanethiolate Complexes: Structural Characterization of (Me2NCH2CH2S)2InX/SR (X = Cl, I; R = 4-MeC6H4S, 4-MeOC6H4S)' Glen G. Briand, Benjamin F.T. Cooper, David B.S. MacDonald, Caleb D. Martin and Gabriele Schatte. Inorganic Chemistry, 2006, 45, 8423-8429. Abstract

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