Reversibility of 1,4-Metal Migration in Cp*RhIII and Cp*IrIII Complexes
Reversibility of 1,4-Metal Migration in Cp*RhIII and Cp*IrIII Complexes
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DOI：
10.1021/om5003232
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发表时间：
2014-05-12
期刊：
影响因子：
2.8
通讯作者：
Ishii, Youichi
中科院分区：
文献类型：
--
作者：
Ikeda, Yousuke;Takano, Koichi;Ishii, Youichi
由2-(间甲苯基)乙烯基络合物[Cp*Rh{C(Ph)=C(C6H4Me-m)Ph}-(PMe3)][BAr4F]从乙烯基向芳基1，4-Rh迁移而形成的(2-乙烯基-4-甲基苯基)芳基罗络合物[Cp*Rh{C6H3-2-(C(Ph)=CHPh)-4-Me}(PMe3)][BAr4F]，，在温和的条件下异构化为区域异构体2-乙烯基苯基配合物[Cp*Rh{C6H4-2-(C-(C6H4Me-m)=CHPh)}(PMe3)][BAr4F]，通过反向反应再生2-(间甲苯基)乙烯基络合物中间体，然后C=C键旋转和第二次1，4-Rh迁移，为乙烯基到芳基1，4-金属迁移的可逆性提供了实验证据。
The (2-ethenyl-4-methylphenyl)arylrhodium complex [Cp*Rh{C6H3-2-(C(Ph)=CHPh)-4-Me}(PMe3)][BAr4F], which is formed from the vinyl-to-aryl 1,4-Rh migration of the 2-(m-tolyl)ethenyl complex [Cp*Rh{C(Ph)=C(C6H4Me-m)Ph}-(PMe3)][BAr4F], is isomerized under mild conditions to the regioisomeric 2-ethenylphenyl complex [Cp*Rh{C6H4-2-(C-(C6H4Me-m)=CHPh)}(PMe3)][BAr4F] by way of a back-reaction to regenerate the 2-(m-tolyl)ethenyl complex intermediate followed by the rotation of the C=C bond and the second 1,4-Rh migration, providing experimental evidence for the reversibility of the vinyl-to-aryl 1,4-metal migration.