Capture of the Complex [Ni(dto)2]2鈥?/sup> (dto2鈥?/sup> = Dithiooxalato Ligand) in a Mo12 Ring: Synthesis, Characterizations, and Application toward the Reduction of Pro

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• 作者：Akram Hijazi ; Justin Claude Kemmegne-Mbouguen ; Se虂bastien Floquet ; Je虂ro虃me Marrot ; Ce虂dric R. Mayer ; Vincent Artero ; Emmanuel Cadot
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：September 19, 2011
• 年：2011
• 卷：50
• 期：18
• 页码：9031-9038
• 全文大小：983K
• 年卷期：v.50,no.18(September 19, 2011)
• ISSN：1520-510X

文摘

The encapsulation of the complex [Ni(dto)₂]^{2鈥?/sup> within an oxothiododecamolybdic cyclic cluster has been investigated. The resulting molybdenum ring, [Mo₁₂O₁₂S₁₂(OH)₁₂(Ni(dto)₂)]2鈥?/sup>, corresponds to the first example of the {Mo₂O₂S₂}-based assembly arranged around a 3d transition-metal complex. It was unambiguously characterized in the solid state and in solution by FT-IR spectroscopy, single-crystal X-ray diffraction, NMR, UV鈥搗isible spectroscopy, and electrospray ionization-high-resolution mass spectrometry (ESI-HRMS). The latter technique revealed to be a powerful tool for the characterization of templated molybdenum ring systems in solution and gave excellent results in high resolution. The electronic spectrum of [Mo₁₂O₁₂S₁₂(OH)₁₂(Ni(dto)₂)]2鈥?/sup> evidenced a strong red shift of the LMCT bands attributed to the complex [Ni(dto)₂]2鈥?/sup>, suggesting significant variations of the electronic properties upon its encapsulation within the Mo₁₂ ring. These differences were demonstrated by electrochemical studies in CH₃CN, which also revealed, for both compounds [Ni(dto)₂]2鈥?/sup> and [Mo₁₂O₁₂S₁₂(OH)₁₂(Ni(dto)₂)]2鈥?/sup>, electrocatalytic properties for the reduction of protons. These results evidence the ability of dithioxalato complexes to act as electrocatalysts for the hydrogen evolution reaction (HER) and confirm such a property for oxothiomolybdenum rings.}