Bis(phosphine) cobalt allyl complexes were used as isolable precursors to access transient, 14-electron cobalt(I) hydrides that promoted the insertion of a series of substituted benzenes. The selectivity of the insertion reaction was assayed by analysis of the resulting diamagnetic 18-electron bis(phosphine)Co(η5-cyclohexadienyl) complexes by multinuclear NMR spectroscopy. Monitoring the insertion of α,α,α-trifluorotoluene (PhCF3) with (R,R)-(iPrDuPhos)CoH by NMR spectroscopy revealed an initially aselective kinetic product mixture that underwent isomerization to the thermodynamically preferred ipso-CF3 product. The site selectivity for ipso-CF3 insertion over alkyl, boryl, and silyl substituents was observed across a series of disubstituted benzenes, motivating an investigation into the kinetic and thermodynamic selectivities of representative alkyl trifluoromethylbenzenes using NMR spectroscopy and X-ray crystallography. Protonation of various cobalt(I) cyclohexadienyl complexes afforded C(sp3)-CF3-substituted cyclohexadienes in high yields, which were trapped by Diels–Alder reactions.
Lebowitz et al. (Thu,) studied this question.