Chisholm, Malcolm H. and Patmore, Nathan J. (2006) Electronic coupling in 1,4-(COS)2C6H4 linked MM quadruple bonds (M = Mo, W): the influence of S for O substitution. Dalton Transactions (26). pp. 3164-3169. ISSN 1477-9226
Metadata only available from this repository.Abstract
Electronic structure calculations employing density functional theory on the compounds [(HCO2)3M2]2(µ-X–C6H4–X) where M = Mo and W and –X = –CO2, –COS and –CS2 reveal that the successive substitution of oxygen by sulfur leads to enhanced electronic coupling as evidenced by the increased energy separation of the metal δ orbital combinations which comprise the HOMO and HOMO−1. This enhanced coupling arises principally from a lowering of the LUMO of the X–C6H4–X bridge which, in turn, increases mixing with the in-phase combination of the M2 δ orbitals. The compounds [(ButCO2)3M2]2(µ-SOC–C6H4–COS), where M = Mo and W, have been prepared from the reactions between M2(O2CBut)4 and the thiocarboxylic acid 1,4-(COSH)2C6H4 in toluene and the observed spectroscopic and electrochemical data indicate stronger electronic coupling of the M2 centers in comparison to the closely related terephthalate compounds.
Item Type: | Article |
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Subjects: | Q Science > Q Science (General) Q Science > QD Chemistry |
Schools: | School of Applied Sciences |
Related URLs: | |
Depositing User: | Sharon Beastall |
Date Deposited: | 03 Apr 2014 08:09 |
Last Modified: | 28 Aug 2021 11:36 |
URI: | http://eprints.hud.ac.uk/id/eprint/19968 |
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