Syntheses of Phosphorus and Sulfur Mixed-Donor Ligands and Their Coordination Chemistry

• Main Authors: Duen-Ren Hou, 侯敦仁
• Other Authors: Shiuh-Tzung Liu
• Format: Others
• Language: zh-TW
• Published: 1994
• Online Access: http://ndltd.ncl.edu.tw/handle/01910394191815452003

碩士 === 國立臺灣大學 === 化學學系 === 82 === Starting from diethyl malonate, [(2-chloromethyl)-3- chloropropyl] phenyl sulfide is synthesized after a series synthetic transforma tion. This sulfide reacts with diisopropyl phosphide to produce a new tripodal ligand: 2-phenylthiomethyl-1,3-bis(diisopropylphosph ino)propane. P2S acts as a bidentate ligand with nickel(II) to form a square planar complex which will be decomplexed by sodium cyanide to regenerate free ligand. A mixed phosphorus and sulfur donor ligand reacts with NiCl2(DME) , (CH3CN)2PdCl2, and (CH3CN)2 PtCl2 to give (PS)MCl2 ( M=Ni, Pd, Pt). The syn isomer of these complexes readily convert into their corresponding anti isomer which is resulted the inversion of sulfur donor center. The inversion barriers were determined.Addi- tion of triphenylphosphine to a solution of (PS)PtCl2, (PS)PdCl2 produces ligand substitution products cis-[(PS)Pt(PPh3)Cl]+ and cis-[(PS)Pd(PPh3)Cl]+ respectively, which undergoes dealkylation reaction at sulfur center to yield {P,S-[C6H4( PPhCH2CH3)(S)]}M- (PPh3)Cl, M=Pd, Pt.