Ionic and covalent mixed-metal complexes by reaction of transition metal M-H acids (M=Mo, Mn, Fe, Co) with [Ir(PMe3)4CH3] or [Rh(PMe3)3CH3] and structurally related Rh-M and Ir-M heterobimetallics (M=Mn, Fe, Ru)

Treatment of [I(PMe3)(4)CH3] with equimolar quantities of the carbonyl hydrides [M(CO)(n)H] (M = Mn, Co; n = 5, 4) or [CpM(CO)(n)] (M = Mo, Fe,- n = 3, 2) resulted in clean protonation of the d(8) substrate producing cis-[I(PMe3)(4)(H)(CH3)[X] where X- = [Mn(CO)(5)](-) (1), [CO(CO)(4)](-)(2), [CpMo(CO)(3)](-) (3), and [CpFe(CO)(2)](-) (4), respectively. Combination of [Rh(PMe3)(3)CH3] with [Mn(CO)(5)H] furnished [(Me3P)(3)Rh(mu-CO)(2)Mn(CO)(3)PMe3] (5), which was also isolated from the salt elimination reaction between [Rh(PMe3)(4)]Cl and Na[Mn(CO)(5)]. [(Me3P)(2)Rh(mu-CO)(2)Fe(PMe3)Cp] (6), [(Me3P)(3)Ir(mu-CO)(2)Fe(PMe3)Cp] (7), and [(Me3P)(3)Ir(mu-CO)(2)Ru(PMe3)Cp] (8) were obtained similarly by reacting [Rh(PMe3)(4)]Cl or [Ir(PMe3)(4)]Cl with the potassium salts K[CpM(CO)(2)] (M = Fe, Ru). The crystal structure analysis of 3 demonstrates that in the solid state the hexacoordinate [Ir(PMe3)(4)(H)(CH3)](+) cation and its [CpMo(CO)(3)](-) counterion exist as well-separated ion pairs. The structures of 5-8 comprise (Me3P)(n)Rh (n = 3, 2) or (Me3P)(3)Ir groups attached to Mn(CO)(3)PMe3 or M(PMe3)Cp fragments (M = Fe, Ru) by doubly carbonyl-bridged metal-metal bonds of normal length: Rh-Mn, 2.6695(14); Rh-Fe, 2.5748(6); Ir-Fe, 2.6470(7); Ir-Ru, 2.7348(14) Angstrom. (C) 2003 Elsevier Science B.V. All rights reserved.