Ni(III)-Thiolate Complexes Stabilized by Phosphine and Carbene Ligand

• Main Authors: Wan, Yi-Chen, 萬易承
• Other Authors: Liaw, Wen-Feng
• Format: Others
• Language: zh-TW
• Published: 2013
• Online Access: http://ndltd.ncl.edu.tw/handle/81654400969673113648

碩士 === 國立清華大學 === 化學系 === 101 === The stable nickel(III) complex [NiIII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (1) was isolated from the reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] and tris(1-pyrrolidinyl) phosphine (P(NC4H8)3). The stable nickel(II) complex [PPN] [NiII(P(NC4H8)3)(P(o-C6H3-3-SiMe3-2-S)3)] (2) was obtained from reduction of Complex 1. Complex 1 and 2 were characterized by UV-vis and single-crystal X-ray diffraction. The stable nickel(III) complexes [NiIII(CNCy)(P(o-C6H3-3-SiMe3-2-S)3)] and [NiIII(CNtBu)(P(o-C6H3-3-SiMe3-2-S)3)] were isolated from the reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] or [NiIII(P(o-C6H3-3-SiMe3-2-S)3)]2 and isocyanide (CNCy or CNtBu). The stable nickel(II) complex [PPN][NiII(CNCy) (P(o-C6H3-3-SiMe3-2-S)3)] (3) and [K-18-crown-6-ether][NiII(CNtBu)(P(o-C6H3-3- SiMe3-2-S)3)] (4) were synthesized by reducing NiIII-CNCy and NiIII-CNtBu. All these complexes were characterized by UV-vis, IR, EPR and single-crystal X-ray diffraction. Using low valence Ni(0) as small molecule activactor, and bipyridine (bipy) as ligand to react with CS2, [(bipy)NiII(η2-CS2)] (5) can be successfully synthesized. Also, using (bipy)Ni0, reduced from (bipy)NiII species by Zn powder, react with CS2 to produce Complex 5.