Syntheses and Characterization of Fe(II) and Cu(I) Complexes Supported by a P2S2 Tetradentate ligand; Biomimetic Complex of Fe-only Hydrogenase

• Main Authors: Chao-ChuanYang, 楊朝銓
• Other Authors: Hua-Fen Hsu
• Format: Others
• Language: en_US
• Published: 2015
• Online Access: http://ndltd.ncl.edu.tw/handle/54060535373851131397

碩士 === 國立成功大學 === 化學系 === 103 === Our research team has been interested in studying the roles of metal sites in metalloproteins. Metal centers with sulfur-rich coordination sphere are present in many metalloproteins, such as hydrogenase, CO dehydrogenase and Metallothioneins. Therefore, we have focused on studying chemistry of metal complexes with sulfur ligation environment to provide the fundamental understanding for the nature of metal sites in biological systems. In this research, a new type of thiolate ligand, tetradentate diphosphine-dithiolate, has been developed. Several metal complexes of this ligand have also been studied. In this thesis, the syntheses of the diphosphine-dithiolate ligand, H2[P2S2*], are described. Several physical methods have been applied to characterize the obtained ligand. Two metal complexes of P2S2* derivatives [Fe(P2S2*)(CO)2] and [Cu2(P2S2*)(PPh3)4]•4CH3OH•H2O are also synthesized and characterized by X-ray crystallography and spectroscopies. [Fe(P2S2*)(CO)2] is a monoiron(II) species. The metal center adopts an octahedral geometry by binding to a P2S2* ligand and two carbonyl ligands. [Cu2(P2S2*)(PPh3)4]•4CH3OH•H2O consists of a dimeric unit and embraces a crystallographic inversion center. Each Cu(I) has a tetrahedral geometry and the coordination sphere is completed by one thiolato group and one phosphine atom of P2S2* ligand, as well as two phosphine atoms from two PPh3 ligands.