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Ligand effects in bimetallic high oxidation state palladium systems

Citation

Ariafard, A and Hyland, CJT and Canty, AJ and Sharma, M and Brookes, NJ and Yates, BF, Ligand effects in bimetallic high oxidation state palladium systems, Inorganic Chemistry, 49, (23) pp. 11249-11253. ISSN 0020-1669 (2010) [Refereed Article]

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Copyright 2010 American Chemical Society

DOI: doi:10.1021/ic1020912

Abstract

Ligand effects in bimetallic high oxidation state systems containing a X-Pd-Pd-Y framework have been explored with density functional theory (DFT). The ligand X has a strong effect on the dissociation reaction of Y to form [X-Pd-Pd](+) + Y(-). In the model system examined where Y is a weak -donor ligand and a good leaving group, we find that dissociation of Y is facilitated by greater -donor character of X relative to Y. We find that there is a linear correlation of the Pd-Y and Pd-Pd bond lengths with Pd-Y bond dissociation energy, and with the -donating ability of X. These results can be explained by the observation that the Pd d(z(2)) population in the PdY fragment increases as the donor ability of X increases. In these systems, the Pd(III)-Pd(III) arrangement is favored when X is a weak -donor ligand, while the Pd(IV)-Pd(II) arrangement is favored when X is a strong -donor ligand. Finally, we demonstrate that ligand exchange to form a bimetallic cationic species in which each Pd is six-coordinate should be feasible in a high polarity solvent.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Ariafard, A (Associate Professor Alireza Ariafard)
Author:Hyland, CJT (Dr Chris Hyland)
Author:Canty, AJ (Professor Allan Canty)
Author:Sharma, M (Dr Manab Sharma)
Author:Brookes, NJ (Dr Nigel Brookes)
Author:Yates, BF (Professor Brian Yates)
ID Code:67268
Year Published:2010
Web of Science® Times Cited:28
Deposited By:Chemistry
Deposited On:2011-03-02
Last Modified:2011-05-03
Downloads:0

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