Carbene complexes. Part 13. The synthesis and characterisation of secondary carbene complexes of vanadium(I), chromium(0), molybdenum(0), tungsten(0), manganese(I), rhenium(I), iron(0), ruthenium(II), cobalt(I), iridium(III), and platinum(IV), and hydridorhodium(III)

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Abstract
(Chloromethylene)dimethylammonium chloride [NMe2(CHCl)]Cl (or its dibromo-analogue) is a convenient source of secondary carbenemetal complexes [M{CH(NMe2)}Ln]. As well as three-fragment oxidative addition to d8 metal complexes (Ru0, lrI, or PtII) to give d6 adducts, two other procedures have been developed: salt elimination from a transition-metallate dianion precursor (V–I, Cr–II, Mo–II, W–II, or Fe–II), and salt elimination with concomitant oxidative addition using a transition-metallate monoanion precursor (Mo0, W0, Mn–I, Re–I, or Co–I). The carbenerhodium(III) complex [{Rh[CH(NMe2)](CO)Cl3}2] reacts with PPh3 in ethanol to yield the hydridocarbene complex [Rh{CH(NMe2)}Cl2H (PR3)2](R = Ph) from which analogues (R3= Et2 or Me2Ph) are accessible. Infrared and 1H or 13C n.m.r. spectra have been used to characterise the 23 new complexes and establish their stereochemistry.