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Radical or not radical: compared structures of metal (M = Ni, Au) bis-dithiolene complexes with a thiazole backbone.

Abstract : A complete series of dianionic, monoanionic, and neutral dithiolene complexes formulated as [Ni(Et-thiazdt)2](n), with n = -2, -1, 0, and Et-thiazdt: N-ethyl-1,3-thiazoline-2-thione-4,5-dithiolate, is prepared using an optimized procedure described earlier for the N-Me derivatives. Electrochemical and spectroscopic properties confirm the electron-rich character of the Et-thiazdt dithiolate ligand. The three complexes are structurally characterized by single-crystal X-ray diffraction. The paramagnetic anionic complex [Ni(Et-thiazdt)2](-1), as Ph4P(+) salt, exhibits side-by-side lateral interactions leading to a Heisenberg spin chain behavior. The solid-state structure of the neutral, diamagnetic [Ni(Et-thiazdt)2](0) complex shows a face-to-face organization with a large longitudinal shift, at variance with the structure of its radical and neutral gold dithiolene analogue described earlier and formulated as [Au(Et-thiazdt)2](•). Comparison of the two structures, and those of the other few structurally characterized pairs of Ni/Au dithiolene complexes, demonstrates the important role played by overlap interactions between gold dithiolene radical species. Despite its closed-shell character, the neutral nickel complex [Ni(Et-thiazdt)2](0) exhibits a semiconducting behavior with a room-temperature conductivity σRT ≈ 0.014 S cm(-1).
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01114502
Contributor : Laurent Jonchère <>
Submitted on : Monday, February 9, 2015 - 3:09:41 PM
Last modification on : Wednesday, October 14, 2020 - 3:43:38 AM

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Agathe Filatre-Furcate, Nathalie Bellec, Olivier Jeannin, Pascale Auban-Senzier, Marc Fourmigué, et al.. Radical or not radical: compared structures of metal (M = Ni, Au) bis-dithiolene complexes with a thiazole backbone.. Inorganic Chemistry, American Chemical Society, 2014, 53 (16), pp.8681-90. ⟨10.1021/ic501293z⟩. ⟨hal-01114502⟩

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