Novel RhCp*/GaCp* and RhCp*/InCp* cluster complexes

The reaction of 6 equivalents of GaCp* (Cp* = pentamethylcyclopentadienyl) with [{Cp* RhCl2}(2)] yields the complex [Cp* Rh(GaCp*)(3)(Cl)(2)] ( 1) exhibting a cage-like intermetallic RhGa3 center with Ga - Cl - Ga bridges. Treatment of this complex with GaCl3 gives the Lewis acid - base adduct [Cp* Rh(GaCp*)(2)(GaCl3)] (2). Reaction of [{Cp* RhCl2}(2)] with understoichiometric amounts of (ECp)-Cp-I* (E = Al, Ga, In) leads to a variety of products strongly dependent on the molecular ratio of the reactants. Thus, the reduction of [{Cp* RhCl2} 2] with one equivalent of EICp* (E = Al, Ga, In) gives the Rh-II dimer [{Cp* RhCl}(2)]. The insertion of 3 equivalents of InCp* into the Rh - Cl bonds of [{Cp* RhCl2}(2)] yields the salt [Cp*Rh-2](+)[Cp* Rh(InCp*){In2Cl4(mu(2)-Cp*)}](-) (3), the anion exhibiting an intermetallic RhIn3 center with an intramolecularly bridging Cp* ring. The reaction of [{Cp* RhCl}(2)] with Cp* Ga yields various insertion products. In trace amount the all hydrocarbon cluster complex [(RhCp*)(2)(GaCp*)(3)] ( 6) is obtained. The corresponding ethylene containing cluster complex [{RhCp(GaCp*)(C2H4)}(2)] (7) can be prepared by treatment of [RhCp*(CH3CN)(C2H4)] with GaCp*.