Assembled Transition Metal Cluster Complexes with Open Shell as Functional Materials

在过渡金属双金属配合物中，观察到由配体pi-体系通过金属d轨道相互作用而形成的新型电子体系。(1)阳离子自由基盐是由轴向磷精配体氧化形成的。对盐类进行了X-射线结构分析。电离导致Rh-Rh键延长0.05，Rh-P键缩短0.12*，表明Rh-Rh键轨道在膦配体上的离域增强。(2)阳离子自由基盐-甲基羟基吡啶配合物的磁化率数据表明，自旋-自旋相互作用是反磁性的(10 cm^~(-1))。(3)用密度泛函方法计算了不同配体的Rh二聚体配合物的阳离子自由基的电子结构。奇电子轨道的对称性和在配体上离域的程度取决于配体。(4)Crys…进一步研究了2-羟基喹啉FITS类大分子桥联配体--镝的阳离子自由基盐的结构、电子结构、磁化率和电导。1)Rh-Rh三角轨道中的奇电子被离域到四个桥联配体的pi轨道上，离域程度达10%。2)桥联配体上的奇电子离域不是在配体的HOMO上，而是HOMO和LUMO的线性组合给出的轨道。3)在含有不同反阴离子和结晶溶剂的阳离子自由基盐晶体中观察到分子间配体-配体(C-C)短接触。测定了自由基阳离子盐的磁化率。对于具有短C-C接触的晶体，其磁化率在低温下服从居里定律和抗磁相互作用。(5)合成了10、11族高核度簇合物，并确定了它们的结构。(6)研究了铂、钯催化锡化反应中间体的结构和异构化反应。较少

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