Mononuclear Ni(III)- / Ni(II)-Thiolate Complexes Coordinated by the Labile Ammonia / Hydrazine Ligands

• Main Authors: Tseng, Yen-Ming, 曾彥銘
• Other Authors: Liaw, Wen-Feng
• Format: Others
• Language: zh-TW
• Published: 2011
• Online Access: http://ndltd.ncl.edu.tw/handle/77352261342126351753

碩士 === 國立清華大學 === 化學系 === 99 === Complex [NiIII(NH3)(P(o-C6H3-3-SiMe3-2-S)3)] (1) was synthesized by reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] and NH3 in 1:10 molar ratio. Besides, addition of 18-crown-6-ether assisted the formation of crystals by hydrogen bonds with terminal NH3 and its bulky sizes. The terminal ligand, NH3, can be easily replaced by the incoming nucleophiles due to its weak bonding compared to the strong interaction between metal center and other ligands bearing negative charges. As a result, taking the advantage of its lability, we could synthesize the expected complexes via replacement. Reaction of [PPN][NiIII(Cl)(P(o-C6H3-3-SiMe3-2-S)3)] and N2H4 (aq) in 1:10 molar ratio afforded [PPN][NiII(N2H4)(P(o-C6H3-3-SiMe3-2-S)3)] (2). [K][NiIII(OH)- (P(o-C6H3-3-SiMe3-2-S)3)] was synthesized by using the lability of NH3 ligand of complex 1. The hydroxyl ligand coordinated to nickel center is also proven to be the key intermediate responsible for the formation of complex 2. Owning to its labile ligand and active electronic environment of complex 2, it could serve as a platform for activation of small molecules. The successful result among small molecules is that purging NO into the solution of complex 2 led to the formation of [PPN][NiIII (NO2)(P(o-C6H3-3- SiMe3-2-S)3)].