Transition Metal Complexes of Unsaturated Cyclic Structures

  • Suzuki Noriyuki
    Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University

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  • 環状不飽和構造を有する遷移金属錯体
  • カンジョウ フホウワ コウゾウ オ ユウスル センイ キンゾク サクタイ

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Abstract

This review describes a series of five-membered metallacyclic compounds of unsaturated carbon-carbon bonds, especially, 1-metallacyclopenta-2,3,4-trienes, 1-metallacyclopent-3-ynes and 1-metallacyclopenta-2,3-dienes on their syntheses, structures and reactivity. Five-membered cyclotrienes andcycloalkynes are prepared from group 4 metal and 1,3-diyne, 1,2,3-butatriene, although cycloallenes have not been synthesized from 1,3-enynes. 1-metallacyclopenta-2,3-dienes are prepared by a few unique methods. These compounds are remarkably stable in spite of their highly strained ring-structure.Some of their molecular structures were even determined by X-ray diffraction study. The 1-metallacyclopenta-2,3,4-trienes and 1-metallacyclopent-3-yneshave a planar metallacycle. The 1-metallacyclpenta-2,3-dienes, on the other hand, have a folded metallacycle and a chiral structure. Some reaction ofthese complexes with borane, aluminum hydride, transition metals and carbonyl compounds are described. Seven membered metallacyclic triene and alkyne areformed when 1,3-diyne or 1,2,3-butatriene coupled with other unsaturated hydrocarbons on the metal. Extended polyynes and cumulenes also form five-membered metallacyclotrienes and alkynes that show “haptotropic” shift.

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