Influence of the Thiazole Backbone on the Structural, Redox, and Optical Properties of Dithiolene and Diselenolene Complexes

Metalation of N-methyl-1,3-thiazoline-2-thione followed by reaction with elemental S or Se affords a simple and efficient approach to N-methyl-1,3-thiazoline-2-thione-4,5-dithiolate (Me-thiazdt) and the diselenolate (Me-thiazds) analogue. In the presence of metal II centers such as Zn, Ni, and Pd th...

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Bibliographic Details
Published in:Inorganic chemistry 2007-12, Vol.46 (25), p.10647-10654
Main Authors: Eid, Samar, Fourmigué, Marc, Roisnel, Thierry, Lorcy, Dominique
Format: Article
Language:English
Subjects:
Chemical Physics
Chemical Sciences
Material chemistry
Physics
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Summary:Metalation of N-methyl-1,3-thiazoline-2-thione followed by reaction with elemental S or Se affords a simple and efficient approach to N-methyl-1,3-thiazoline-2-thione-4,5-dithiolate (Me-thiazdt) and the diselenolate (Me-thiazds) analogue. In the presence of metal II centers such as Zn, Ni, and Pd these ligands afford the corresponding dianionic dithiolene and diselenolene complexes. The Ni and Pd dianionic complexes are easily oxidized into the monoanionic species. Complexes were isolated and characterized by single-crystal X-ray crystallography. Most often a substitutional S/N−Me disorder is observed, attributable to the square-planar trans complexes disordered on two positions or coexistence of both cis and trans isomers on inversion centers. Monoanionic complexes exhibit a strong NIR absorption band with ε values up to 33 750 M-1 cm-1.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic7013682