橋かけしたケイ素、ゲルマニウム配位子が拓く錯体化学

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タイトル別名
  • Coordination Chemistry Pioneered by Bridging Si- and Ge-Ligands
  • Award Accounts 橋かけしたケイ素、ゲルマニウム配位子が拓く錯体化学
  • Award Accounts ハシカケシタ ケイソ 、 ゲルマニウム ハイイシ ガ ヒラク サクタイ カガク

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<p>Transition metal complexes, having the coordination bonds with strong covalent-bond characters, undergo various bondforming reactions, similar to the organo-transition metal complexes with a metal-carbon s-bond. This article reviews recent studies by the author and his co-workers on the multinuclear complexes of group 10 transition metal complexes having bridging Si- and Ge-ligands. Triangular triplatinum(0) complexes having three bridging diarylsilylene ligands are newly prepared, and undergo skeletal rearrangement on addition of alkynes. The complex with SiPh2 ligands catalyzes hydrosilylation of aromatic aldehydes and ketones with H2SiPh2. Detailed studies on the dipalladium and diplatinum complexes with bridging Si- and Geligands revealed unique chemical properties, such as activation of the Si–H bond of the ligand as well as bond forming reactions of the bridging germylene with germyl ligands. Tetra-, penta-, hexa-, and octa-nuclear Pd and Pt complexes with the bridging silylene and germylene ligands are obtained from heating a mixture of the metal-phosphine complexes, precursor of the Si- and Ge-ligands, and scavenger of the auxiliary ligands. Thus formed complexes react with metal halides and with the Si- and Gecompounds to produce new multinuclear transition metal complexes. The reactions occur reversibly because of kinetic lability of the multinuclear complexes with the bridging Si- and Ge-ligands.</p>

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