Carbon−Oxygen Bond Formation between a Terminal Alkoxo Ligand and a Coordinated Olefin. Evidence for Olefin Insertion into a Rhodium Alkoxide

Preparation and reactivity of a series of bis(phosphine) rhodium(I) alkoxides stabilized by intramolecular olefin coordination are reported. {Rh(PEt3)2[kappa1:eta2-OCRR'(CH2)nCH=CH2]} (n = 1, 2) were prepared via alcoholysis of {Rh(PEt3)2[N(SiMe3)2]} by the corresponding alcohols HOCRR'(CH2)nCH=CH2. The in situ generated {Rh(PEt3)2[kappa1:eta2-OCRR'(CH2)2CH=CH2]} were not stable at ambient temperatures and decomposed in the presence of added PEt3 to afford 2,2-disubstituted-5-methylenetetrahydrofurans and [(PEt3)4Rh-H] in good to high yields. Kinetic and deuterium labeling results support a syn-oxyrhodation pathway via direct olefin insertion into a Rh-O bond, followed by rapid beta-hydride elimination. In comparison, {Rh(PEt3)2[kappa1:eta2-OCRR'CH2CH=CH2]} are isolated as stable crystals, and the Rh-olefin interactions are evidenced by an X-ray structure. Heating of these complexes generated [Rh(PEt3)2(eta2-allyl)] and the corresponding ketones in high yields following an apparent beta-allyl elimination pathway.