Hirotsu Masakazu, Sanou Junhei, Nakae Toyotaka, Matsunaga Takumi, Kinoshita Isamu
Department of Chemistry, Faculty of Science, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa, 259-1293, Japan.
Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan.
Acta Crystallogr E Crystallogr Commun. 2022 Apr 22;78(Pt 5):500-505. doi: 10.1107/S2056989022003954. eCollection 2022 May 1.
The thiol-ate nickel complexes {2-[({2-[(2-amino-ethyl-κ)(meth-yl)amino-κ]eth-yl}imino-κ)meth-yl]benzene-thiol-ato-κ}nickel(II) chloride, [Ni(CHNS)]Cl (), and [2-({[2-(piperazin-1-yl-κ , )eth-yl]imino-κ}meth-yl)benzene-thiol-ato-κ]nickel(II) hexa-fluoro-phosphate di-chloro-methane monosolvate, [Ni(CHNS)]PF·CHCl (), were synthesized by the reactions of 2-(-butyl-thio)-benzaldehyde, tri-amines, and nickel(II) salts. Both complexes have a nickel ion surrounded by an ,','',-tetra-dentate ligand, forming a square-planar geometry. The terminal ,-chelating moiety is ,-di-alkyl-ethane-1,2-di-amine for and 1-alkyl-piperazine for . The N-Ni-N bite angle in the terminal ,-chelate ring in [76.05 (10)°] is much smaller than that in [86.16 (6)°]. Cyclic voltammograms of and in aqueous media indicated that the reduction and oxidation potentials of are more positive than those of . The smaller bite angle of the terminal piperazine chelate in reduces the electron-donating ability of the tetra-dentate ligand, resulting in a positive shift of the redox potentials. Both complexes exhibit catalytic activity for proton reduction, and the piperazine moiety in is effective in reducing the overpotential.
硫醇盐镍配合物{2-[({2-[(2-氨基乙基-κ)(甲基)氨基-κ]乙基}亚氨基-κ)甲基]苯硫醇盐-κ}镍(II)氯化物，[Ni(CHNS)]Cl ()，以及[2-({[2-(哌嗪-1-基-κ ，)乙基]亚氨基-κ}甲基)苯硫醇盐-κ]镍(II)六氟磷酸盐二氯甲烷单溶剂合物，[Ni(CHNS)]PF·CHCl ()，通过2-(叔丁基硫代)苯甲醛、三胺和镍(II)盐的反应合成。两种配合物都有一个被 ，','',-四齿配体包围的镍离子，形成平面正方形几何结构。末端 ，-螯合部分对于 是 ，-二烷基乙烷-1,2-二胺，对于 是1-烷基哌嗪。 [76.05 (10)°]中末端 ，-螯合环的N-Ni-N咬角比 [86.16 (6)°]中的小得多。 和 在水介质中的循环伏安图表明， 的还原和氧化电位比 的更正。 中末端哌嗪螯合物较小的咬角降低了四齿配体的给电子能力，导致氧化还原电位正向移动。两种配合物都表现出对质子还原的催化活性，并且 中的哌嗪部分在降低过电位方面是有效的。
