Inorganic Chemistry, Vol.55, No.13, 6794-6798, 2016
A Heterobimetallic W-Ni Complex Containing a Redox-Active W[SNS](2) Metalloligand
The tungsten complex W[SNS](2) ([SNS]H-3 = 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](2)Ni(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](2)Ni(dppe) catalyzes the electrochemical reduction of protons to hydrogen coincident with the first reduction of the complex.