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Assembled Transition Metal Cluster Complexes with Open Shell as Functional Materials

开壳组装过渡金属簇配合物作为功能材料

基本信息

批准号：
07555573
负责人：
KAWAMURA Takashi
金额：
$ 1.54万
依托单位：
GIFU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555573/
关键词：
cluster complex ionic radical magnetism crystal structure odd-electron distribution rhodium aromatic ligand metal-metal bond 不対電子軌道共役

项目摘要

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

在过渡金属双金属配合物中，如铑与π共轭桥联配体的配合物，观察到配体π体系通过金属d轨道相互作用而形成的新的电子体系。(1)通过氧化铑二聚体配合物与轴向膦配体生成阳离子自由基盐。用X-射线衍射法对盐的结构进行了分析。电离诱导Rh-Rh键延长0.05和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)铑二聚体配合物与甲基羟基吡啶配体的阳离子自由基盐的磁化率数据表明，自旋-自旋相互作用是抗磁性的（10 cm ↑ [3]）。<-1>(3)用密度泛函方法计算了铑与不同配体形成的二聚体配合物阳离子自由基的电子结构。奇电子轨道的对称性和离域到配体上的程度取决于配体。(4)哭泣 ...更多信息研究了2-羟基喹啉FIT类似物二铑与大π共轭桥联配体阳离子自由基盐的结构、电子结构、磁化率和电导。1)Rh-Rh δ ^**-轨道中的奇电子离域到四个桥连配体的π轨道上达到10%的程度。2)桥连配体上奇电子的离域不是在配体的HOMO上，而是在HOMO和LUMO的线性组合所给出的轨道上。3）在阳离子自由基盐与各种抗衡阴离子和结晶溶剂的晶体中观察到分子间配体-配体（C-C）短接触。测量了自由基阳离子盐的磁化率。在低温下，短接触晶体的磁化率服从居里定律，并存在抗磁相互作用。(5)合成了第10族和第11族的高核簇合物，并测定了它们的结构。(6)研究了Pt和Pd催化的锡烷基化反应中反应中间体的结构和异构化。少