The Chemistry of Linkages between Main Group Elements and Transition Metals

为了建立主族元素与过渡金属之间化学键的新基本概念，本文探索了以下六个主题。(1)主族元素与过渡金属之间的饱和键（F.Ozawa）。制备了一系列含烷基、硅基、香叶基和锡基配体的铂（II）配合物，并通过x射线衍射分析、核磁共振波谱和动力学实验对其结构和对炔插入和还原消除的反应性进行了研究。(2)过渡金属配合物与元素间键反应的理论研究（S.Sakaki）。用从头算MO方法研究了Si-B， Si-C和Si-Si键对铂(0)或钯(0)配合物的氧化加成。Si-C和Si-Si键的反应通过一种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键合和反应特性（K.Tatsumi）。利用C-Y键裂解反应合成了一系列单核的、6族的、更多的金属硫族化合物。所得到的Cp^*MY_3型配合物（Y=O， S, Se）作为过渡金属簇的通用构建块。(4)过渡金属催化双硼的反应（N.Miyaura）。过渡金属催化二硼化合物活化是合成有机硼化合物的有效途径，是有机合成中用途广泛的中间体。这些反应包括不饱和烃的二硼化、二硼与有机卤化物的交叉偶联以及有机硼酸与烯酮的共轭加成。(5)主要元素与过渡金属的不饱和键（H.Tobita）。用铑、铱、铁、钌等多种晚期过渡金属制备了碱稳定硅烯配合物，并对其结构和反应进行了系统的研究。有些配合物以C=O和C=N双键进行环加成。(6)硫酸盐和硅基配体的金属转化（k.o osakada）。通过对中间体的x射线衍射分析和反应动力学，获得了标题反应的机理细节。镉的μ-硅基络合物就是一个显著的例子。少

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