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The Chemistry of Linkages between Main Group Elements and Transition Metals

主族元素与过渡金属键合的化学

基本信息

批准号：
09239105
负责人：
OZAWA Fumiyuki
金额：
$ 57.28万
依托单位：
OSAKA CITY UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 2000
项目状态：
已结题

项目摘要

The following six subjects have been explored to establish new basic concepts for chemical bonding between main group elements and transition metals.(1) Saturated Linkages between Main Group Elements and Transition Metals (F.Ozawa). A series of platinum (II) complexes bearing alkyl, silyl, germyl, and stannyl ligands have been prepared, and their structures and reactivities towards alkyne-insertion and reductive elimination have been examined by X-ray diffraction analysis, NMR spectroscopy, and kinetic experiments.(2) Theoretical Study of the Reactions between Transition Metal Complexes and Inter-element Linkages (S.Sakaki). Oxidative addition of Si-B, Si-C, and Si-Si bonds towards a platinum (0) or palladium (0) complex has been examined by means of ab initio MO methods. The reactions of Si-C and Si-Si bonds proceed via an unusual non-planar transition state.(3) Bonding and Reactions Characteristics of Early Transition Metal Chalcogenides (K.Tatsumi). A series of mononuclear, group 6 … More metal chalcogenides have been synthesized by the use of C-Y bond cleaving reactions. The resulting Cp^*MY_3 type complexes (Y=O, S, Se) serve as versatile building blocks of transition metal clusters.(4) Transition Metal-catalyzed Reactions of Diborons (N.Miyaura). Transition-metal catalyzed activation of diboron compounds is an efficient way of synthesizing organoboron compounds which are versatile intermediates in organic synthesis. The reactions include diboration of unsaturated hydrocarbons, cross-coupling between diborons and organic halides, and conjugate addition of organoboronic acids to enones.(5) Unsaturated Linkages between Main Elements and Transition Metals (H.Tobita). Base-stabilized silylene complexes have been prepared with a variety of late transition metals including rhodium, iridium, iron, and ruthenium, and a systematic study has been carried our for their structures and reactions. Some of the complexes undergo cycloaddition with C=O and C=N double bonds.(6) Transmetallation of Thiolate and Silyl Ligands (K.Osakada). Mechanistic details of the title reaction have been gained by X-ray diffraction analysis of intermediates and reaction kinetics. A μ-silyl complex of dirhodium is a remarkable example. Less

为了建立主族元素与过渡金属间化学键的新的基本概念，对以下六个课题进行了探索。(1)主族元素和过渡金属之间的饱和键（F.Ozawa）。制备了一系列含烷基、甲硅烷基、甲锗烷基和甲锡烷基配体的铂（II）配合物，并通过X射线衍射分析、核磁共振谱和动力学实验研究了它们的结构和对炔插入和还原消除的反应活性。(2)过渡金属络合物与元素间键合反应的理论研究（S.Sakaki）。用从头算方法研究了Si-B、Si-C和Si-Si键与铂（0）、钯（0）配合物的氧化加成反应。Si-C和Si-Si键的反应通过一个不寻常的非平面过渡态进行。(3)早期过渡金属硫族化合物的成键和反应特性。一系列单核细胞，第6组 ...更多信息金属硫属化物已经通过使用C-Y键断裂反应合成。所得的Cp^*MY_3型配合物（Y=O，S，Se）是过渡金属簇合物的多功能结构单元。(4)过渡金属催化的二硼反应（N.Miyaura）。过渡金属催化活化二硼化合物是合成有机硼化合物的有效方法，有机硼化合物是有机合成中的重要中间体。这些反应包括不饱和烃的二硼化反应、二硼与有机卤化物的交叉偶联反应以及有机硼酸与烯酮的共轭加成反应。(5)主要元素和过渡金属之间的不饱和键（H.Tobita）。以铑、铱、铁、钌等后过渡金属为原料，合成了碱稳定的硅烯配合物，并对其结构和反应进行了系统的研究。一些配合物与C=O和C=N双键发生环加成反应。(6)硫醇盐和甲硅烷基配体的金属交换（K.Osakada）。通过对中间体的X射线衍射分析和反应动力学研究，得到了反应机理的详细信息。二铑的μ-甲硅烷基配合物就是一个显著的例子。少