Assembled Transition Metal Cluster Complexes with Open Shell as Functional Materials

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In transition metal dimetal complexes as dirhodium one with pi-conjugated bridging ligands, formation of novel electronic system which was constructed by ligand pi-systems interacting through metal d-orbitals is observed. (1) Cationic radical salts were generated by oxidation of rhodium dimer complexes with axial phospfine ligands. X-ray structure analysis of the salts were carried out. The ionization induced elongation of Rh-Rh bond by 0.05 and shortening of Rh-P bond by 0.12* , showing enhanced delocalization of the Rh-Rh bonding orbital onto the phosphine ligands. (2) Magnetic susceptibility data of a cationic radical salt of rhodium dimer complex with methylhydroxypyridine ligands indicated that spin-spin interaction was diamagnetical (10 cm^<-1>). (3) Electronic structure of cationic radical of rhodium dimer complexes with various ligands were calculated by DFT method. The symmetry of odd-electron orbital and the extent of delocalization onto ligand depend on the ligands. (4) Crys … More tal structure, electronic structure, magnetic susceptibility, and electric conductance of cationic radical salts of dirhodium complexes with large pi-conjugated bridging ligands, 2-hydroxyquinoline fits analogues, were investigated. 1) The odd-electron in the Rh-Rh delta^<**>-orbital is delocalized onto pi-orbitals of the four bridging ligands to the extent of 10%. 2) The delocalization of the odd-electron on the bridging ligand is not onto the HOMO of the ligand, but the orbital given by a linear combination of the HOMO and the LUMO.3) Intermolecular ligand-ligand (C-C) short contact was observed in the crystals of cationic radical salts with various counter anion and crystalline solvent. Magnetic susceptibility of the radical cation salts were measured. Magnetic susceptibility obeys Curie law with diamagnetic interaction at low temperature for the crystals with short C-C contacts. (5) High nuclearity cluster complexes of group 10 and 11 were prepared and their structure were determined. (6) Structure and isomerization of a reaction intermediate in Pt- and Pd-catalized stannylation reaction were studied. Less