Thienyl carboxylate ligands bound to and bridging MM quadruple bonds, M = Mo or W: Models for polythiophenes incorporating MM quadruple bonds

Matthew J. Byrnes, Malcolm H. Chisholm, Robin J.H. Clark, Judith C. Gallucci, Christopher M. Hadad, Nathan J. Patmore

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

A series of compounds of the form [M2L4] and [{( tBuCO2)3M2}2(μ- L′)] have been made where M = Mo or W, L = a thienyl, bithienyl, or terthienyl carboxylate, and L′ = a corresponding thienyl dicarboxylate. The electronic absorption spectra are reported and the electronic structures discussed. Intense metal-to-ligand charge transfer bands traverse the visible and near-IR regions of the electronic absorption spectrum. The compounds show reversible metal-based oxidations and quasireversible ligand-based reductions. The molecular structure of Mo2(O2C-2-Th) 4·2THF is reported, on the basis of a single crystal X-ray diffraction study. These compounds provide insight into the expected properties of related dimetalated polythiophenes incorporating MM quadruple bonds.

LanguageEnglish
Pages6334-6344
Number of pages11
JournalInorganic Chemistry
Volume43
Issue number20
Early online date1 Sep 2004
DOIs
Publication statusPublished - 1 Oct 2004
Externally publishedYes

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electronic spectra
carboxylates
Absorption spectra
Metals
Ligands
absorption spectra
ligands
metals
Molecular structure
Electronic structure
Charge transfer
molecular structure
charge transfer
Single crystals
electronic structure
X ray diffraction
Oxidation
oxidation
single crystals
diffraction

Cite this

Byrnes, Matthew J. ; Chisholm, Malcolm H. ; Clark, Robin J.H. ; Gallucci, Judith C. ; Hadad, Christopher M. ; Patmore, Nathan J. / Thienyl carboxylate ligands bound to and bridging MM quadruple bonds, M = Mo or W : Models for polythiophenes incorporating MM quadruple bonds. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 20. pp. 6334-6344.
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Thienyl carboxylate ligands bound to and bridging MM quadruple bonds, M = Mo or W : Models for polythiophenes incorporating MM quadruple bonds. / Byrnes, Matthew J.; Chisholm, Malcolm H.; Clark, Robin J.H.; Gallucci, Judith C.; Hadad, Christopher M.; Patmore, Nathan J.

In: Inorganic Chemistry, Vol. 43, No. 20, 01.10.2004, p. 6334-6344.

Research output: Contribution to journalArticle

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T2 - Inorganic Chemistry

AU - Byrnes, Matthew J.

AU - Chisholm, Malcolm H.

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AB - A series of compounds of the form [M2L4] and [{( tBuCO2)3M2}2(μ- L′)] have been made where M = Mo or W, L = a thienyl, bithienyl, or terthienyl carboxylate, and L′ = a corresponding thienyl dicarboxylate. The electronic absorption spectra are reported and the electronic structures discussed. Intense metal-to-ligand charge transfer bands traverse the visible and near-IR regions of the electronic absorption spectrum. The compounds show reversible metal-based oxidations and quasireversible ligand-based reductions. The molecular structure of Mo2(O2C-2-Th) 4·2THF is reported, on the basis of a single crystal X-ray diffraction study. These compounds provide insight into the expected properties of related dimetalated polythiophenes incorporating MM quadruple bonds.

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