[M(GaCp*)4] (M = Pd, Pt) as building blocks for dimeric homoleptic cluster compounds of the type [MPt(GaCp*)5]

The monomeric homoleptic Pt(O) complex [Pt(GaCp*)(4)] (1) has been synthesized by reaction of [Pt(COD)(2)] with GaCp* in hexane. The monomeric homoleptic NO complexes [Pd(GaCp*)(4)] (2) and [Pd{InC(SiMe3)(3)}(4)] (3) are accessible by reaction of [Pd(tmeda)(CH3)(2)] with GaCp* and [InC(SiMe3)(3)], respectively. These reactions were shown to proceed via methyl group transfer from palladium to indium. or gallium, respectively. Complexes 1 and 2 can be used as building blocks for the synthesis of dinuclear cluster compounds. Thus, reaction of [Pt(COD)(2)] with 1 or 2 and subsequent addition of GaCp* yields [Pt-2(GaCp*)(2)(mu(2)-GaCp*)(3)] (4a) and [PtPd(GaCp*)(mu(2)-GaCp*)(3)] (5a). Intermediates of this dimerization reactions, i.e., [Pt-2(GaCp*)(mu(2)-GaCp*)(3)(eta(2)-COD)] (4b) and [PtPd(GaCp*)(mu(2)-GaCp*)(3)(eta(2)-COD)](5b), were isolated and characterized by means of variable-temperature NMR spectroscopy.