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Scission of Carbon Monoxide Using TaR3, R = (N(tBu)Ph) or OSi(tBu)3: a DFT Investigation


Brookes, NJ and Ariafard, A and Stranger, R and Yates, BF, Scission of Carbon Monoxide Using TaR3, R = (N(tBu)Ph) or OSi(tBu)3: a DFT Investigation, Chemistry: A European Journal, 16, (27) pp. 8117-8132. ISSN 0947-6539 (2010) [Refereed Article]

DOI: doi:10.1002/chem.200903348


The experimentally known reduction of carbon monoxide using a 3-coordinate [Ta(silox)3] (silox = OSi-(tBu)3) complex initially forms a ketenylidene [(silox)3Ta-CCO], followed by a dicarbide [(silox)3Ta-CC-Ta-(silox)3] structure. The mechanism for this intricate reaction has finally been revealed by using density functional theory, and importantly a likely structure for the previously unknown intermediate [(silox)3Ta-CO]2 has been identified. The analysis of the reaction pathway and the numerous intermediates has also uncovered an interesting pattern that results in CO cleavage, that being scission from a structure of the general form [(silox)3Ta-C nO] in which n is even. When n is odd, cleavage cannot occur. The mechanism has been extended to consider the effect of altering both the metal species and the ligand environment. Specifically, we predict that introducing electron-rich metals to the right of Ta in the periodic table to create mixed-metal dinuclear intermediates shows great promise, as does the ligand environment of the Cummins-style 3-coordinate amide structure. This latter environment has the added complexity of improved electron donation from amide rotation that can significantly increase the reaction exothermicity. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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:Brookes, NJ (Dr Nigel Brookes)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:67753
Year Published:2010
Funding Support:Australian Research Council (DP0986529)
Web of Science® Times Cited:6
Deposited By:Chemistry
Deposited On:2011-03-07
Last Modified:2011-05-04

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