Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)2 (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)5M=C(oEt)Ar] (Ar= Ph, M = Cr, W; Ar = 2-MeC6H4, 2-MeOC6H4, M = W)

The reaction of the arylated Fischer carbene complexes [(CO)5M=C(OEt)Ar] (Ar=Ph; M = Cr, W; 2-MeC6H4; 2-MeOC6H; M = W) with the phosphaalkenes RP=C(NMe2), (R=tBu, SiMe3) afforded the novel phosphaalkene complexes [[RP=C(OEt)Ar]M(CO)5] in addition to the compounds [(RP=C(NMe2)2]M(CO)5]. Only in the case of the R = SiMe3 (E/Z) mixtures of the metathesis products were obtained. The bis(dimethylamino)methylene unit of the phosphaalkene precursor was incorporated in olefins of the type (Me2N)2C=C(OEt)(Ar). Treatment of [(CO)5W=C(OEt)(2-MeOC6H4)] with HP=C(NMe2)2 gave rise to the formation of an E/Z mixture of [[(Me2N)2CH-P=C(OEt)(2-MeOC6H4)]W(CO)5] the organophosphorus ligand of which formally results from a combination of the carbene ligand and the phosphanediyl [P-CH(NMe2)2]. The reactions reported here strongly depend on an inverse distribution of alpha-electron density in the phosphaalkene precursors (Pdelta Cdelta+), which renders these molecules powerfu] nucleophiles.