Radical or Not Radical: Compared Structures of Metal (M = Ni, Au) Bis-Dithiolene Complexes with a Thiazole Backbone

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• 作者：Agathe Filatre-Furcate ; Nathalie Bellec ; Olivier Jeannin ; Pascale Auban-Senzier ; Marc Fourmigu茅 ; Antoine Vacher ; Dominique Lorcy
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：August 18, 2014
• 年：2014
• 卷：53
• 期：16
• 页码：8681-8690
• 全文大小：532K
• ISSN：1520-510X

文摘

A complete series of dianionic, monoanionic, and neutral dithiolene complexes formulated as [Ni(Et-thiazdt)₂]ⁿ, with n = 鈭?, 鈭?, 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鈥揗e 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]^鈭?, 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]^{鈥?/sup>. 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 蟽_RT 鈮?0.014 S cm鈥?.}