d-pi Interaction in Transition Metal Cluster Complexes and Their Properties

过渡金属簇配合物中的 d-pi 相互作用及其性质

基本信息

批准号：
09650900
负责人：
KAWAMURA Takashi
金额：
$ 2.11万
依托单位：
GIFU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

Transition metal cluster complexes of rhodium and iridium with aromatic or chloro bridging ligands have been prepared, their structure and physicochemical properties have been studied and following results have been obtained.1. The reaction of dinuclear rhodium complexes with silyl chlorides gave new type of tetranuclear rhodium complexes with chloro-bridges.2. The symmetry and delocalization of the singly occupied molecular orbitals (SOMO) of rhodium dinuclear complexes were shown to be heavily dependent on ligands based on X-ray structures and DFT theoretical calculations. A large mixing ofsiguma_<RhRh> and n_p orbitals were observed for Rh_2^<5+> complexes with axial phosphine ligands. The pi_<RhRh>* orbital is localized on the metal atoms and the orbital is moderately delocalized onto the pi system of the bridging ligands.3. Diiridium complexes with bridging aminopyridine ligands were shown to have low oxidation potentials and short metal-metal separations.4. The delta* SOMO of Rh_2^<5+> complexes with hydroxypyridine ligands were shown to be delocalized onto the aromatic bridging ligands to the extent of about 10 %. In crystal, Rh_2^<4+> and Rh_2^<5+> complexes were packed with pi stacked arrangement of aromatic bridgeing ligands. Electric conductance of some of Rh_2^<5+> complexes were in the order of 10^<-7> S cm^<-1> (room temperature, pellets). Magnetism of crystals of Rh_2^<5+> complexes with aromatic bridging ligands were analyzed in relation to their crystal stucture.5. Square planar Pd(II) and Pt(II) complexes with silyl or stannyl and phosphine ligands showed facile twist-rotational unimolecular isomerization.

已经制备了与芳香族或氯颗桥接配体的犀牛和虹膜簇的过渡金属簇复合物，已经研究了它们的结构和物理化学特性，并获得了以下结果。1。二核菱形复合物与甲硅烷基氯化物的反应给出了新型的四核菱形配合物与氯桥的反应。2。基于X射线结构和DFT理论计算，表明单一占据的分子轨道（SOMO）的对称和离域化很大程度上取决于配体。对于与轴向磷酸配体的RH_2^<5+>复合物，观察到了大量的siguma_ <hrh>和N_P轨道。 pi_ <rhrh>*轨道位于金属原子上，轨道被适度地定位到桥接配体的PI系统上。3。与桥接氨基吡啶配体的二维岛配合物显示出低氧化电位和短的金属金属分离。4。 rh_2^<5+>复合物与羟基吡啶配体的Delta* Somo被证明将其定位到芳族桥接的配体上，其程度约为10％。在晶体中，将rh_2^<4+>和RH_2^<5+>配合物装满了芳族桥配体的PI堆叠布置。某些RH_2^<5+>复合物的电导率为10^<-7> s cm^<-1>（室温，颗粒）。分析了与晶体的晶体配体的RH_2^<5+>复合物晶体的磁性相对于它们的晶体稳定性。5。与甲硅烷基或stannyl和磷酸配体的方形平面PD（II）和PT（II）配合物显示出易于旋转的单分子异构化。