Abstract
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-(η(5)-cyclohexadienyl) complexes by multinuclear NMR spectroscopy. Monitoring the insertion of α,α,α-trifluorotoluene (PhCF(3)) with [(R,R)-((iPr)DuPhos)-CoH] by NMR spectroscopy revealed an initially aselective kinetic product mixture that underwent isomerization to the thermodynamically preferred ipso-CF(3) product. The site selectivity for ipso-CF(3) 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-(sp(3))-CF(3)-substituted cyclohexadienes in high yields, which were trapped by Diels-Alder reactions.