Heteroleptic nickel complexes bearing O‐methyldithiophosphate and aminodiphosphine monosulfide ligands as robust molecular electrocatalysts for hydrogen evolution. (23rd May 2022)

• Record Type: Journal Article
• Authors: Chen, Luo; Xie, Bin; Li, Tao; Lai, Chuan; Cao, Jia‐Xi; Ji, Ren‐Wu; Liu, Meng‐Nan; Li, Wei; Zhang, Dong‐Liang; He, Jia‐Yu
• Is Part Of: Applied organometallic chemistry. Volume 36:Number 7(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-23
• Subjects: aminodiphosphine monosulfide -- crystal structure -- electrocatalytic hydrogen evolution -- nickel complex -- O‐methyldithiophosphate; Organometallic chemistry -- Periodicals; Organometallic compounds -- Periodicals; 547.05
• DOI: 10.1002/aoc.6725
• Languages: English
• ISSNs: 0268-2605

Abstract

Abstract : Five new heteroleptic nickel complexes containing O‐methyldithiophosphate and aminodiphosphine monosulfide ligands, [Ni((PPh2 )({S}PPh2 )NR)(S2 P{O}OCH3 )] (R = (CH2 )4 CH3 (1 ), (CH2 )3 OCH3 (2 ), (CH2 )3 SCH3 (3 ), (CH2 )2 CH(CH3 )2 (4 ), and C6 H4 CH3 –4 (5 )), were synthesized by two different methods at room temperature. All complexes were characterized by elemental analysis, spectroscopy ( 1 H, 13 C, 31 P nuclear magnetic resonance [NMR], and ultraviolet–visible [UV–vis]), single crystal X‐ray diffraction as well as thermogravimetric analysis. In the crystal structures of 1 –4 and 5 ⋅CH2 Cl2, the nickel atom locates in a slightly distorted square‐planar coordination by one phosphorous atom and three sulfur atoms from the aminodiphosphine monodulfide and O‐meyldithiophosphate ligands. Furthermore, their electrochemical behaviors and electrocatalytic performances for the reduction proton to hydrogen have also been evaluated by the cyclic voltammetry using trifluoroacetic acid (TFA) as the proton source. With the addition of 120 mM TFA to MeCN solution of 1 –5 (1.0 mM), the turnover frequencies are estimated to be 494–706 s −1, and the corresponding overpotentials are 0.61–0.70 V versus Fc + /Fc, respectively. This finding diagnoses that the heteroleptic nickel complexes can serve as robust and effective molecular electrocatalysts for hydrogen evolution. Abstract : Heteroleptic nickel complexes [Ni((PPh2 )({S}PPh2 )NR)(S2 P{O}OCH3 )] synthesized by two different methods serve as robust and effective molecular electrocatalysts for hydrogen evolution with TOFs of 494–706 s −1 and overpotentials of 0.61–0.70 V.