A novel heterobimetallic complex with the formula W[SNS]2Ni(dppe) ([SNScat]H3 = bis(2-mercapto-p-tolyl)amine and dppe = 1,2-bis(diphenylphosphino)ethane) was prepared from (dppe)NiCl2 and the previously reported W[SNS]2 coordination complex under reducing conditions. X-ray diffraction reveals a pseudo-tetrahedral nickel and a pseudo-octahedral tungsten with a formal Ni–W bond at a distance of 2.54 Å. Electrochemical studies reveal a species with readily accessible reduction potentials at −1.43 and −2.14 V vs [Cp2Fe]0/+. The complex is a catalyst for the electrochemical reduction of protons to hydrogen with an overpotential of 700 mV, a TOF of 14 s–1, and a faradaic efficiency of 80±3 % using 4-cyanoanilinium tetrafluoroborate as the acid source.

Electrochemical proton reduction using a redox-active W[SNS]2 cofactor tethered to a Ni center

251st National Meeting (2016)

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