Thienyl Carboxylate Ligands Bound to and Bridging MM Quadruple Bonds, M = Mo or W:  Models for Polythiophenes Incorporating MM Quadruple Bonds

A series of compounds of the form [M2L4] and [{( t BuCO2)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...

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Bibliographic Details
Published in:Inorganic chemistry 2004-10, Vol.43 (20), p.6334-6344
Main Authors: Byrnes, Matthew J, Chisholm, Malcolm H, Clark, Robin J. H, Gallucci, Judith C, Hadad, Christopher M, Patmore, Nathan J
Format: Article
Language:English
Subjects:
Carboxylic Acids - chemistry
Crystallography, X-Ray
Hydrogen Bonding
Ligands
Models, Chemical
Molecular Structure
Molybdenum - chemistry
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Thiophenes - chemical synthesis
Thiophenes - chemistry
Tungsten - chemistry
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Summary:A series of compounds of the form [M2L4] and [{( t BuCO2)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.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic040086n