Coordination Chemistry of Ga(C₅Me₄Ph): Novel Homoleptic d¹⁰ Cluster Complexes of Palladium^†

The synthesis and characterization of the novel sterically encumbered Ga(I) ligand GaCp*Ph (1b) (Cp*Ph = C5Me4Ph) is presented. GaCp*Ph reacts with the Pd(0) source Pd2(dvds)3 (dvds = tetramethyldivinyldisiloxane) to give the trinuclear cluster [Pd3(GaCp*Ph)(μ2-GaCp*Ph)(μ3-GaCp*Ph)2(dvds)] (2a). 2a is the first example of a Ga(I)-containing cluster with a potentially labile olefinic ligand. It was found that 2a is an intermediate in the formation of the dinuclear cluster [Pd2(GaCp*Ph)2(μ2-GaCp*Ph)3] (2b), which is formed on reaction of 2a with GaCp*Ph. Both clusters were found to be labile toward GaCp*, AlCp*, or phosphines, giving substitution products in all cases.