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Insight into the Mechanism of R-R Reductive Elimination from the Six-Coordinate d6 Complexes L2Pt(R)4 (R = vinyl, Me)

Citation

Ariafard, A and Ejehi, Z and Sadrara, H and Mehrabi, T and Etaati, S and Moradzadeh, A and Moshtaghi, M and Nosrati, H and Brookes, NJ and Yates, BF, Insight into the Mechanism of R-R Reductive Elimination from the Six-Coordinate d6 Complexes L2Pt(R)4 (R = vinyl, Me), Organometallics, 30, (3) pp. 422-432. ISSN 0276-7333 (2011) [Refereed Article]


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Copyright Statement

Copyright 2011 American Chemical Society

DOI: doi:10.1021/om1005512

Abstract

We have used density functional theory to investigate the reductive elimination from platinum(IV) structures of the form L(2)PtR(4) where L = PMe(3), PH(3), PF(3), CO, NH(3) and R = vinyl, Me. We conclude that reductive elimination occurs via the L-predissociation pathway for R = Me, irrespective of ligand L. But when R = vinyl, direct elimination is the preferred pathway if the L ligand is PMe(3); otherwise both pathways are competitive for R = vinyl. We also note that if L is more pi-electron accepting and less a-electron donating, the reductive elimination from the six-coordinate complexes L(2)PtR(4) will be more rapid. Reductive elimination from the five-coordinate complexes LPtR(4) proceeds more easily if the ligand trans to the two R groups being coupled is more a-electron donating and the ligands cis to the two R groups are more pi-electron accepting.

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:Brookes, NJ (Dr Nigel Brookes)
Author:Yates, BF (Professor Brian Yates)
ID Code:72715
Year Published:2011
Web of Science® Times Cited:18
Deposited By:Chemistry
Deposited On:2011-08-31
Last Modified:2014-05-08
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