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Activation of CS2 and CS by ML3 Complexes

Citation

Ariafard, A and Brookes, NJ and Stranger, R and Yates, BF, Activation of CS2 and CS by ML3 Complexes, Journal of the American Chemical Society, 130, (36) pp. 11928-11938. ISSN 0002-7863 (2008) [Refereed Article]

DOI: doi:10.1021/ja800946e

Abstract

The aim of this study was to determine the best neutral ML3 metal complexes for activating and cleaving the multiple bonds in CS2 and CS. Current experimental results show that, so far, only one bond in CS2 can be cleaved, and that CS can be activated but the bond is not broken. In the work described in this paper, density functional theory calculations have been used to evaluate the effectiveness of different ML 3 complexes to activate the C-S bonds in CS2 and CS, with M = Mo, Re, W, and Ta and L = NH2. These calculations show that the combination of Re and Ta in the L3Re/CS2/TaL3 complex would be the most promising system for the cleavage of both C-S bonds of CS2. The reaction to cleave both C-S bonds is predicted to be exothermic by about 700 kJ mol-1 and to proceed in an almost barrierless fashion. In addition, we are able to rationalize why the breaking of the C-S bond in CS has not been observed experimentally with M = Mo: this reaction is strongly endothermic. There is a subtle interplay between charge transfer and π back-donation, and it appears that the Mo-C and Mo-S bonds are not strong enough to compensate for the breaking of the C-S bond. Our results suggest that, instead, CS could be cleaved with ReL3 or, even better, with a combination of ReL3 and TaL3. Molecular orbitale and Mulliken charges have been used to help explain these trends and to make predictions about the most promising systems for future experimental exploration. © 2008 American Chemical Society.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal 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:55271
Year Published:2008
Web of Science® Times Cited:30
Deposited By:Chemistry
Deposited On:2009-03-08
Last Modified:2009-05-01
Downloads:0

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