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由二苯基-2-吡啶基膦和氢化物桥联的均二金属和异二金属配合物的合成与反应性：炔烃插入不饱和M1(μ-PPh2Py)(μ-H)2M2部分的区域选择性。

Synthesis and reactivity of homo- and hetero-dimetallic complexes bridged by diphenyl-2-pyridylphosphine and hydrides: regioselectivity of alkyne insertion into unsaturated M1(micro-PPh2Py)(micro-H)2M2 moieties.

作者信息

Takahashi Yoshinori, Murakami Naoaki, Fujita Ken-Ichi, Yamaguchi Ryohei

机构信息

Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.

出版信息

Dalton Trans. 2009 Mar 21(11):2029-42. doi: 10.1039/b815890h. Epub 2009 Jan 30.

DOI:10.1039/b815890h
PMID:19259574
Abstract

New homo- and hetero-dimetallic complexes bridged by diphenyl-2-pyridylphosphine and hydrides [(CpIr)(micro-PPh(2)Py)(mu-H)(2)(MCp)]OTf (: M = Ir, n = 2; : M = Rh, n = 2; : M = Ru, n = 1) were synthesized. The reactions of with terminal alkynes gave micro-vinyl complexes [(CpIr)(micro-PPh(2)Py)(micro-H)(micro-C(R)=CH(2))(IrCp)]OTf (: R = H; : R = CO(2)Me; : R = Ph) and [(CpIr)(micro-PPh(2)Py)(micro-H)(micro-CH[double bond, length as m-dash]CHR)(IrCp)]OTf (: R = SiMe(3); R = Ph). The reactions of with alkynes gave [(CpIr)(micro-PPh(2)Py)(micro-H)(micro-C(R)=CH(2))(RhCp)]OTf (: R = H; : R = CO(2)Me; : R = Ph), two of which are in equilibrium with [(CpIr)(mu-PPh(2)Py)(micro-H)(micro-CH(2)=C(CO(2)Me))(RhCp)]OTf () and [(CpIr)(micro-PPh(2)Py)(micro-H)(micro-CH(2)=C(Ph))(RhCp)]OTf () at 50 degrees C, respectively. The reactions of with alkynes gave [(CpIr)(micro-PPh(2)Py)(micro-H)(micro-CH(2)=C(R))(RuCp)][OTf] (: R = CO(2)Me; : R = Ph). Plausible pathways for the insertion of alkynes to the metal-hydride bonds and the interconversion of the micro-vinyl complexes are discussed. Structures of the cationic parts of 3, 8, 9, 13b, 14b and 15b have been confirmed by X-ray analysis.

摘要

合成了由二苯基-2-吡啶基膦和氢化物桥连的新型同核和异核双金属配合物[(CpIr)(μ-PPh₂Py)(μ-H)₂(MCp)][OTf]ₙ（：M = Ir，n = 2；：M = Rh，n = 2；：M = Ru，n = 1）。其与末端炔烃的反应生成了μ-乙烯基配合物[(CpIr)(μ-PPh₂Py)(μ-H)(μ-C(R)=CH₂)(IrCp)][OTf]₂（：R = H；：R = CO₂Me；：R = Ph）和[(CpIr)(μ-PPh₂Py)(μ-H)(μ-CH=CHR)(IrCp)][OTf]₂（：R = SiMe₃；R = Ph）。其与炔烃的反应生成了[(CpIr)(μ-PPh₂Py)(μ-H)(μ-C(R)=CH₂)(RhCp)][OTf]₂（：R = H；：R = CO₂Me；：R = Ph），其中两种在50℃时分别与[(CpIr)(μ-PPh₂Py)(μ-H)(μ-CH₂=C(CO₂Me))(RhCp)][OTf]₂（）和[(CpIr)(μ-PPh₂Py)(μ-H)(μ-CH₂=C(Ph))(RhCp)][OTf]₂（）处于平衡状态。其与炔烃的反应生成了[(CpIr)(μ-PPh₂Py)(μ-H)(μ-CH₂=C(R))(RuCp)][OTf]（：R = CO₂Me；：R = Ph）。讨论了炔烃插入金属-氢键以及μ-乙烯基配合物相互转化的可能途径。3、8、9、13b、14b和15b阳离子部分的结构已通过X射线分析得到证实。

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