Electronic coupling in 1,4-(COS)2C6H4 linked MM quadruple bonds (M = Mo, W): The influence of S for O substitution

Malcolm H. Chisholm, Nathan J. Patmore

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Abstract

Electronic structure calculations employing density functional theory on the compounds [(HCO2)3M2]2(-X-C 6H4-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(-SOC-C6H4-COS), where M = Mo and W, have been prepared from the reactions between M2(O2CBu t)4 and the thiocarboxylic acid 1,4-(COSH) 2C6H4 in toluene and the observed spectroscopic and electrochemical data indicate stronger electronic coupling of the M 2 centers in comparison to the closely related terephthalate compounds.

Original languageEnglish
Pages (from-to)3164-3169
Number of pages6
JournalDalton Transactions
Issue number26
Early online date6 Apr 2006
DOIs
Publication statusPublished - 5 Jul 2006
Externally publishedYes

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