Synthesis of Novel Heteroleptic Oxothiolate Ni(II) Complexes and Evaluation of Their Catalytic Activity for Hydrogen Evolution

Abstract

Two heteroleptic nickel oxothiolate complexes, namely [Ni(bpy)(mp)] (1) and [Ni(dmbpy)(mp)] (2), where mp = 2-hydroxythiophenol, bpy = 2,2′-bipyridine and dmbpy = 4,4′-dimethyl-2,2′-bipyridine were synthesized and characterized with various physical and spectroscopic methods. Complex 2 was further characterized by single crystal X-ray diffraction data. The complex crystallizes in the monoclinic P 21/c system and in its neutral form. The catalytic properties of both complexes for proton reduction were evaluated with photochemical and electrochemical studies. Two different in their nature photosensitizers, namely fluorescein and CdTe-TGA-coated quantum dots, were tested under various conditions. The role of the electron donating character of the methyl substituents was revealed in the light of the studies. Thus, catalyst 2 performs better than 1, reaching 39.1 TONs vs. 4.63 TONs in 3 h, respectively, in electrochemical experiments. In contrast, complex 1 is more photocatalytically active than 2, achieving a TON of over 6700 in 120 h of irradiation. This observed reverse catalytic activity suggests that HER mechanism follows different pathways in electrocatalysis and photocatalysis.

Keywords

• hydrogen evolution
• nickel complexes
• heteroleptic complexes
• electrocatalysts
• photocatalysts