A Heterobimetallic W–Ni Complex Containing a Redox-Active W[SNS]2 Metalloligand

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• 作者：Kyle E. Rosenkoetter ; Joseph W. Ziller ; Alan F. Heyduk
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 5, 2016
• 年：2016
• 卷：55
• 期：13
• 页码：6794-6798
• 全文大小：269K
• 年卷期：0
• ISSN：1520-510X

文摘

The tungsten complex W[SNS]₂ ([SNS]H₃ = bis(2-mercapto-4-methylphenyl)amine) was bound to a Ni(dppe) [dppe = 1,2-bis(diphenylphosphino)ethane] fragment to form the new heterobimetallic complex W[SNS]₂Ni(dppe). Characterization of the complex by single-crystal X-ray diffraction revealed the presence of a short W–Ni bond, which renders the complex diamagnetic despite formal tungsten(V) and nickel(I) oxidation states. The W[SNS]₂ unit acts as a redox-active metalloligand in the bimetallic complex, which displays four one-electron redox processes by cyclic voltammetry. In the presence of the organic acid 4-cyanoanilinium tetrafluoroborate, W[SNS]₂Ni(dppe) catalyzes the electrochemical reduction of protons to hydrogen coincident with the first reduction of the complex.