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Theoretical studies of the oxidative addition of azolium salts to a model Wilkinson's catalyst
Citation
Hawkes, KJ and McGuinness, DS and Cavell, KJ and Yates, BF, Theoretical studies of the oxidative addition of azolium salts to a model Wilkinson's catalyst, Dalton Transactions, (16) pp. 2505-2513. ISSN 1477-9226 (2004) [Refereed Article]
DOI: doi:10.1039/b407088g
Abstract
The oxidative addition of 1,3-dimethylimidazolium to a model Wilkinson's catalyst (RhCl(PH3)3) has been studied with density functional calculations (B3LYP). According to our free energy calculations, the octahedral rhodium carbene hydride product forms from initial predissociation of a phosphine molecule to subsequently form a 5 ligand intermediate; however, results indicate that a six ligand, associative route with a concerted three-centred transition structure may also be competitive. Exchange of the phosphine molecule on the metal centre with trimethylphosphine had a significant effect in lowering the barrier to oxidative addition and decreasing the endothermicity of the reaction. Solvation was found to have a moderate effect on the overall reaction. Bulk solvent calculations reflected a relative stabilisation of reactants for both pathways, resulting in an endothermic overall reaction. A study of alternative azolium salts revealed the saturated 1,3-dimethy1-4,5-dihydroimidazolium resulted in little change to the reaction geometries or energies, while the use of 3-methylthiazolium salt significantly reduced the barrier to addition and increased the exothermicity of the reaction considerably.
Item Details
Item Type: | Refereed Article |
---|---|
Research Division: | Chemical Sciences |
Research Group: | Inorganic chemistry |
Research Field: | Organometallic chemistry |
Objective Division: | Expanding Knowledge |
Objective Group: | Expanding knowledge |
Objective Field: | Expanding knowledge in the chemical sciences |
UTAS Author: | Hawkes, KJ (Dr Kirsty Hawkes) |
UTAS Author: | McGuinness, DS (Dr David McGuinness) |
UTAS Author: | Cavell, KJ (Professor Kingsley Cavell) |
UTAS Author: | Yates, BF (Professor Brian Yates) |
ID Code: | 31986 |
Year Published: | 2004 |
Web of Science® Times Cited: | 21 |
Deposited By: | Chemistry |
Deposited On: | 2004-08-01 |
Last Modified: | 2011-09-30 |
Downloads: | 0 |
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