[M(GaCp*)₄] (M = Pd, Pt) as Building Blocks for Dimeric Homoleptic Cluster Compounds of the Type [MPt(GaCp*)₅]

Abstract

The monomeric homoleptic Pt(0) complex [Pt(GaCp*) 4 ] ( 1 ) has been synthesized by reaction of [Pt(COD) 2 ] with GaCp* in hexane. The monomeric homoleptic Pd(0) complexes [Pd(GaCp*) 4 ] ( 2 ) and [Pd{InC(SiMe 3 ) 3 } 4 ] ( 3 ) are accessible by reaction of [Pd(tmeda)(CH 3 ) 2 ] with GaCp* and [InC(SiMe 3 ) 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 (μ 2 -GaCp*) 3 ] ( 4a ) and [PtPd(GaCp*)(μ 2 -GaCp*) 3 ] ( 5a ). Intermediates of this dimerization reactions, i.e., [Pt 2 (GaCp*)(μ 2 -GaCp*) 3 (η 2 -COD)] ( 4b ) and [PtPd(GaCp*)(μ 2 -GaCp*) 3 (η 2 -COD)] ( 5b ), were isolated and characterized by means of variable-temperature NMR spectroscopy.