Synthesis, Structure, and Electrochemical Properties of O‐Alkyldithiophosphato Nickel Complexes with Chelating Aminodiphosphine Ligands

• Published in: European journal of inorganic chemistry 2018-05, Vol.2018 (17), p.1817-1823
• Main Authors: Deng, Chenglong, Wang, Zheng, Xie, Ying, He, Jiao, Wei, Juan, Zou, Like, Xie, Bin, Jiang, Jin, Wu, Yu, Ma, Zhongyi, Hu, Mengyuan, Li, Yulong, Zhao, Peihua, Liu, Xufeng
• Format: Article
• Language: English
• Subjects: Aminodiphosphine ligands; Chelation; Coordination compounds; Crystallography; Cyclic voltammetry; Electrocatalysis; Electrochemical analysis; Fourier transforms; Hydrogen production; Hydrogenase; Inorganic chemistry; Ligands; Nickel; NMR; Nuclear magnetic resonance; O,O′‐alkydithiophosphoric acid; X‐ray diffraction
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201800092

Eight new O‐alkyldithiophosphato nickel complexes 1–8 with chelating aminodiphosphine ligands have been successfully synthesized in moderate yields by the treatment of O,O′‐alkydithiophosphoric acid salts (R1O)2P{S}SH·Et2NH (R1 = CH3, CH2CH3) with nickel aminodiphosphine precursors Ni[(Ph2P)2NR2]Cl2 [R2 = (CH2)3OCH3, (CH2)3SCH3, (CH2)2CH(CH3)2, CH(CH3)C6H5] in the presence of Et3N at room temperature. Meanwhile, reactions of Ni(S2P{OR1}2)2 and aminodiphosphine ligands (Ph2P)2NR2 in CHCl3 solvents at room temperature also resulted in the formation of the target complexes 1–8 in satisfactory yields. The two synthetic routes are found to be efficient pathways to prepare O‐alkyldithiophosphato nickel complexes with chelating aminodiphosphine ligands. All the new complexes were fully characterized by elemental analysis, FTIR and NMR (1H, 13C, 31P) spectroscopy, and particularly for three of them by X‐ray crystallography. Moreover, these complexes were found to be catalysts for hydrogen production in the presence of a weak acid under electrochemical conditions. The reactions of (R1O)2P{S}SH·Et2NH with Ni[(Ph2P)2NR2]Cl2 and the reactions of Ni(S2P{OR1}2)2 with (Ph2P)2NR2 Ni(S2P{O}OR1)[(Ph2P)2NR2] were performed. These simple reactions provide new and efficient ways to O‐alkyldithiophosphato nickel complexes with chelating aminodiphosphine ligands.