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

Research output: Contribution to journalArticle

28 Citations (Scopus)

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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Toluene
Sulfur
Electronic structure
Density functional theory
Substitution reactions
Metals
Oxygen
Acids
terephthalic acid

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title = "Electronic coupling in 1,4-(COS)2C6H4 linked MM quadruple bonds (M = Mo, W): The influence of S for O substitution",
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.",
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Electronic coupling in 1,4-(COS)2C6H4 linked MM quadruple bonds (M = Mo, W) : The influence of S for O substitution. / Chisholm, Malcolm H.; Patmore, Nathan J.

In: Dalton Transactions, No. 26, 05.07.2006, p. 3164-3169.

Research output: Contribution to journalArticle

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T1 - Electronic coupling in 1,4-(COS)2C6H4 linked MM quadruple bonds (M = Mo, W)

T2 - The influence of S for O substitution

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N2 - 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.

AB - 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.

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