1,4- and 1,3-Metal Migration in a Cp*IrIII Complex: Experimental Evidence of Direct 1,3-Metal Migration
作者： Yousuke Ikeda , Koichi Takano , Shintaro Kodama , Youichi Ishii
DOI: 10.1021/OM5005258
关键词:
摘要: Reactions of the phenyliridium(III) complex [Cp*IrCl(Ph)(PMe3)] with internal alkynes (RC≡CR, R = Ph or Me) in presence NaBArF4 give rise to formation (o-vinylaryl)iridium complexes [Cp*Ir{o-C6H4C(R)═CHR}(PMe3)][BArF4] (2a, Ph; 2b, via alkyne insertion and subsequent vinyl-to-aryl 1,4-miration Ir(III) center, while a similar reaction PhC≡CMe affords π-allyl [Cp*Ir{η3-CH(Ph)C(Ph)CH2}(PMe3)][BArF4] (4) high yield. The latter is formal 1,3-Ir migration product formed from vinyliridium [Cp*Ir{C(Ph)═C(Me)Ph}(PMe3)][BArF4] (3c). Deuterium labeling experiments have revealed that this produced by two distinct mechanisms, (1) C═C bond rotation 3c, followed direct migration, (2) successive aryl-to-allyl 1,4-Ir migrations way o-vinylaryl [Cp*Ir{o-C6H4C(Me)═CHPh}(PMe3)][BArF4] (2c). This provides first experimental evidence 1,3-metal migratio...
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