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，我们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合(F.Ozawa)。合成了一系列含烷基、硅基、Germyl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)过渡金属配合物与元素间键反应的理论研究(S.Sakaki)。用从头算方法研究了Si-B、Si-C和Si-Si键与铂(0)或钯(0)络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)早过渡金属硫族化合物(K.TatSumi)的成键和反应特征。一系列单核、第6族…利用C-Y键裂解反应合成了更多的金属硫系化合物。得到的Cp^*My_3型络合物(Y=O，S，Se)是过渡金属簇合物的通用构件。(4)过渡金属催化的Diborons(N.Miyaura)反应。过渡金属催化活化二硼化合物是合成有机合成中用途广泛的中间体有机硼化合物的有效方法。这些反应包括不饱和碳氢化合物的二硼化合，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之间的不饱和键(H.Tobita)。用多种后过渡金属，包括Rh、Ir、Fe和Ru制备了碱稳定的硅烯配合物，并对它们的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)硫酸酯和硅基配体(K.Osakada)的转金属反应。通过对中间体的X-射线衍射分析和反应动力学分析，得到了该反应的机理细节。一个值得注意的例子是μ-硅基的镝的络合物。较少

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