Transition Metal Catalysis Involving Cleavages of .SIGMA.-Bonds between Group 14 Elements and Characterization of Metal Complexes Relevant to the Catalyst Intermediates.

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  • １４族元素間σ結合の開裂を伴う錯体触媒反応と触媒活性種関連錯体の挙動
  • 14ゾク ゲンソ カン シグマ ケツゴウ ノ カイレツ オ トモナウ サクタイ ショクバイ ハンノウ ト ショクバイ カッセイシュ カンレン サクタイ ノ キョドウ

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Some homogeneous transition metal catalysts are highly active to cleave σ-bonds between group 14 elements under mild reaction conditions. Various unsaturated compounds insert into the a-bonds to afford a wide variety of products having the group 14 elements. We have utilized silylstannanes (Si-Sn), disilanes (Si-Si), and distannanes (Sn-Sn) in the presence of a transition metal catalyst to realize 1, 4-silylstannation of 1, 3-dienes, 1, 2-silylstannation of olefins, dimerization and bis-silylation of 1, 3-dienes, 1, 4-carbosilylation of 1, 3-dienes, silylation of allylic esters, and bisstannylation of 1, 3-dienes. The structures and fluxional behavior of cis-bis (stannyl) bis (phosphine) platinum, cis-bis (silyl) bis (phosphine) platinum, and cis-bis (stannyl) bis (phosphine) palladium complexes were examined. In the fluxional process, all the spin-spin couplings are retained. The fluxionality is attributed to unimolecular twist-rotation via a pseudotetrahedral transition state.

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