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