om3009537_si_002.pdf (40.05 kB)
Intermolecular Methyl Group Exchange and Reversible P–Me Bond Cleavage at Cobalt(III) Dimethyl Halide Species
journal contributionposted on 2016-02-19, 23:28 authored by Hongwei Xu, Paul G. Williard, Wesley H. Bernskoetter
The cobalt(III) dimethyl halide complexes cis,mer-(PMe3)3Co(CH3)2X (X = Cl, I) were found to undergo a degenerate cobalt-to-cobalt transfer of the methyl ligands during isotopic labeling experiments. Extensive mechanistic studies exclude radical, methyl iodide elimination, and disproportionation/comproportionation pathways for exchange of the methyl groups between metals. A related cobalt(III) dimethyl complex supported by the tridentate phosphine ligand MeP(CH2CH2PMe2)2 showed dramatically slower methyl ligand transfer, indicative of a mechanism for intermetallic exchange with a requisite phosphine dissociation. Crossover experiments between cobalt(III) dimethyl halide complexes supported by PMe3 and MeP(CH2CH2PMe2)2 are consistent with a dicobalt transition structure in which only one cobalt center requires phosphine dissociation prior to methyl transfer. An additional methyl group scrambling process between cis,mer-(PMe3)3Co(CH3)2I and free PMe3 was also identified during the investigation and originates from reversible P–CH3 bond cleavage.