Activation of H
<sub>2</sub>
and CO by Sulfur‐Rich Nickel Model Complexes for [NiFe] Hydrogenases and CO Dehydrogenases
作者:Dieter Sellmann、Raju Prakash、Frank W. Heinemann
DOI:10.1002/ejic.200300786
日期:2004.5
Reactions of the trinuclear complexes [Ni(RS3)]3 [HS32− = bis(2-mercaptophenyl)sulfide(2−) (1a) or siS32− = bis(2-mercapto-3-trimethylsilylphenyl)sulfide(2−) (1b)] with nucleophiles L (L = NHPnPr3, NHPCy3, NHSPh2, PnPr3) afforded the corresponding mononuclear complexes [Ni(L)(RS3)] [R = si = SiMe3; L = NHPnPr3 (2b); L = NHPCy3 (3a,b); L = NHSPh2 (4a,b); L = PnPr3 (5a)]. X-ray structural determinations
三核配合物 [Ni(RS3)]3 [HS32− = 双 (2-巯基苯基) 硫化物 (2−) (1a) 或 siS32− = 双 (2-巯基-3-三甲基甲硅烷基苯基) 硫化物 (2−) ( 1b)] 与亲核试剂 L (L = NHPnPr3, NHPCy3, NHSPh2, PnPr3) 得到相应的单核配合物 [Ni(L)(RS3)] [R = si = SiMe3; L = NHPnPr3 (2b);L = NHPCy3 (3a,b);L = NHSPh2 (4a,b);L = PnPr3 (5a)]。X 射线结构测定表明,2b、3a、3b、4a 和 5a 显示出四面体扭曲的平面 [Ni(L)(RS3)] 碎片。配合物 2b 通过分子间 N-H···N 氢键二聚化。与 2b 相比,配合物 3a 和 4a 在硫醇基团和 NH 质子之间表现出分子内氢键。配合物 2-4 具有弱酸性 NH 质子,并与