The Coordination Chemistry of Heavy p-Block Metals

The overall goal of our research is the development of the coordination chemistry of the heavy p-block 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:

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.

MeInSNNS     indium bis-thiolate 2     (NNS)2In2(OMe)Cl3

‘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.  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.

Dimethylpy        Dimethylbipy


‘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).
PhS3InPPh3        InPtga

‘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.

BisdimethylaminoInOMerxn   BisdimethylaminoInOMe

'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

*Student authors are bolded