Structure and Reactivity of Half-Sandwich Rh(+3) and lr(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives

摘要

Traditional rhodium carbene chemistry relies on the controlled decomposition of diazo derivatives with [Rh_(2)(OAc)_(4)] or related dinuclear Rh(+2) complexes, whereas the use of other rhodium sources is much less developed. It is now shown that half-sandwich carbene species derived from [Cp*MX_(2)]_(2) (M = Rh, Ir; X = Cl, Br, I, Cp* = pentamethylcyclopentadienyl) also exhibit favorable application profiles. Interestingly, the anionic ligand X proved to be a critical determinant of reactivity in the case of cyclopropanation, epoxide formation and the previously unknown catalytic metathesis of azobenzene derivatives, whereas the nature of X does not play any significant role in −OH insertion reactions. This perplexing disparity can be explained on the basis of spectral and crystallographic data of a representative set of carbene complexes of this type, which could be isolated despite their pronounced electrophilicity. Specifically, the donor/acceptor carbene 10a derived from ArC(═N_(2))COOMe and [Cp*RhCl_(2)]_(2) undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh–Cl bond with formation of the C-metalated rhodium enolate 11 . In contrast, the analogous complexes 10b , c derived from [Cp*RhX_(2)]_(2) (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl_(2)]_(2) are sufficiently stable and allow true carbene reactivity to be harnessed. These complexes are competent intermediates for the catalytic metathesis of azobenzene derivatives, which provides access to α-imino esters that would be difficult to make otherwise. Rather than involving metal nitrenes, the reaction proceeds via aza-ylides that evolve into diaziridines; a metastable compound of this type has been fully characterized.