Crystal structure and electrocatalytic investigation of diiron azadiphosphine complex [Fe₂(μ-pdt)(CO)₄{(μ-Ph₂P)₂NH}] related to [FeFe]-hydrogenases

Abstract

The solid-state structure of diiron azadiphosphine complex [Fe₂(μ-pdt)(CO)₄{(μ-Ph₂P)₂NH}] (1) bearing a pendant amine, which can be regarded as the diiron subsite model of [FeFe]-hydrogenases, have been well investigated by X-ray crystallography. Notably, in order to explore the potential role of a pendant amine in the bridging azadiphosphine ligand, the electrochemical and electrocatalytic properties of 1 and its reference analog [Fe₂(μ-pdt)(CO)₄{(μ-Ph₂P)₂CH₂}] (2) have been studied and compared in the absence and presence of acetic acid (HOAc) as a proton source using cyclic voltammetry (CV), indicating that they are active for the electrocatalytic proton reduction to hydrogen (H₂).

Keywords:

• Diiron complexes
• azadiphosphine
• pendant amine
• crystal structure
• electrocatalytic proton reduction

Additional information

Funding

This work was financially supported by the Natural Science Foundation of Shanxi Province (No. 201701D121035), the Scientific and Technologial Innovation Programs of Higher Education Institutions in Shanxi Province (No. 201802078), and the Scientific Research Foundation for the Returned Overseas Chinese Scholars of Shanxi Province for the financial support of this work.