MOLECULAR DESIGN AND SYNTHESIS OF COMPOSITE BI-AND POLY-NUCLEAR COMPLEXES.

Research Project

Project/Area Number	06640731
Research Category	Grant-in-Aid for General Scientific Research (C)
Allocation Type	Single-year Grants
Research Field	Inorganic chemistry
Research Institution	OSAKA CITY UNIVERSITY
Principal Investigator	KINOSHITA Isamu OSAKA CITY UNIVERSITY,DEPARTMENT OF CHEMISTRY,ASSOCIATE PROFESSOR, 理学部, 助教授 (80128735)
Co-Investigator(Kenkyū-buntansha)	KITANO OSAKA PREFECTURAL COLLEGE OF TECHNOLOGY,DEPARTMENT OF LIBERAL ARTS LECTURER, 講師 (20234263)
Project Period (FY)	1994 – 1995
Project Status	Completed (Fiscal Year 1995)
Budget Amount *help	¥2,100,000 (Direct Cost: ¥2,100,000) Fiscal Year 1995: ¥600,000 (Direct Cost: ¥600,000) Fiscal Year 1994: ¥1,500,000 (Direct Cost: ¥1,500,000)
Keywords	MIXED METAL COMPLEX / PLATINUM (II) / CHROMIUM (III) / ONE DIMENSIONAL STRUCTURE / HELIX / VANADIUM (IV) / BINUCLEAR COMPLEX / 光学活性 / バナジウム / クロム / 白金 / 金属間相互作用
Research Abstract	In this research, the composite binuclear complex was prepared from [Pt (4-mpyt) _4] ^<2+> using the metal incorporating ability of this complex. The late transition metals as Ni (II) and Co (II) can be incorporated in this system with moderate yield. Both complexes have square planar structure for Pt (II), and tetragonal pyramidal either for Ni (II) and Co (II). The apical ligation to Co or Ni contribute for the stabilization of the system. Both complexes increase the inter metallic interaction upon oxidation to d^7-d^7 system, formally no apparent interaction present for the system. Especially, [Pt^<III> (4-mpyt) _4Co^<II>X] has strong inter metallic interaction causing diamagnetism as a result. The early transition metals can be incorporated in the form of its oxides as V=O or Cr=O.Especially, Cr (IV) has quite unique coordination sphere in this system that never happened in the mononuclear system. Furthermore, Cr (III) complex, [Pt (4-mpyt) _4Cr^<III>Cl], is surrounded by five ligating atoms with square pyramidal fashion that never appeared in Cr (III) state. The x-ray structural results show the evidence as follows. (1) Regardless of early or late, first transition metals can form [Pt (4-mpyt) _4MX] molecule. Four N atoms coordinate to first transition metals due to the hard metal preference compared to the soft S atoms. (3) In the case of [Pt (4-mpyt) _4Cr=O] or [Pt (4-mpyt) _4V=O], the complexes are crystallizes in the space group P4/ncc. As a result, the inter-molecular linkage through molecular 4 fold axis forms crystallographic 4 fold axis and making up the one dimensional system. Dipyridine disulfide formed by the oxidation of pyridine thiol is widely used as a bio assay reagent or the synthet