Properties and Reactions of Coordinatively Unsaturated Organometallics

本计画的目的是研究配位不饱和有机金属簇合物的结构、电子态、反应活性及性质。本项目的研究揭示了过渡金属簇合物的配位不饱和度与配体、金属原子和氧化态的关系，具体如下：1。通过双核锰羰基配合物的光脱羰化反应，合成了配位不饱和双核锰配合物。X-射线结构测定的起始和所得的配合物表明，配位不饱和是伴随着金属-金属键的多重性的增加。研究了不饱和双核配合物与几种配体分子的缔合平衡。计算了各平衡点的焓变和熵变.一种新的双核铂（II）配合物的晶体结构表明，金属原子的线性链状排列。 ...更多信息 铂配合物在溶液中表现出自缔合平衡。结合配合物的电子结构对这些现象进行了分析。配合物的氧化诱导了自缔合倾向的增加。ESR研究表明，四羧酸二铑及其类似物中Rh-Rh键的电子构型与配体有关。根据配体对氧化电位的依赖性，分析了电子相互作用对氧化电位的依赖性.研究了新合成的钴铑混合三核簇合物的分子结构和电化学行为。当铑原子数增加时，单电子氧化发生在更正的电位下，单电子还原发生在更负的电位下.用从头算SCF MO方法计算了氢在镍表面化学吸附的电子结构，并用相互作用前线轨道方法进行了分析。少

The purpose of this project has been to investigate structures, electronic states, reactivities, and properties of coordinatively unsaturated organometallic cluster complexes. Studies under this project has revealed dependences of coordinative unsaturation of transition-metal cluster complexes on ligands, metal atoms, and oxidation states as follows:1. A coordinatively unsaturated dinuclear manganese complex was prepared by photo-decarnonylation of a dinuclear manganese carbonyl complex. X-ray structure determination of both of the starting and resulting complexes showed that the coordinative unsaturation is accompanied by an increase of the multiplicity of the metal-metal bond. Studies are carried out on associative equilibria of the unsaturated dinuclear complex with several selected ligand molecules. Changes in enthalpy and entropy for the equilibria have been evaluated.2. Crystal structure of a new dinuclear platinum(II) complex showed a linear chain arrangement of the metal atoms. … More The platinum complex showed a self-association equilibrium in solutions. These phenomena are anylysed in connection with the electronic structure of the complex. Oxidation of the complex induced an increase of the tendency of the self-association.3. ESR studies have showen that the electronic configuration of the Rh-Rh bond in dirhodium tetracarboxylates and their analogs are ligand dependent. The electronic interactions for the dependence were analyzed on the basis of ligand dependence of their oxidation potentials.4. Studies were carried out on molecular structure and electrochemical behavior of newly prepared cobalt-rhodium mixed trinuclear cluster complexes. When the number of rhodium atom is increased, the one-electron oxidation takes place at a more positive potential and the one-electron reduction occurs at a more negative potential.5. Electronic structure of chemisorption of dihydrogen on nickel surfaces were calculated with an abinitio SCF MO method and analyzed with the interacting-frontier orbital method. Less