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 E(I)Cp*(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 E(I)Cp*(E = Al, Ga, In) gives the RhII dimer {Cp*RhCl}2]. The insertion of 3 equivalents of InCp* into the Rh-Cl bonds of {Cp*RhCl2}2] yields the salt Cp*2Rh]+Cp*Rh(InCp*){In2Cl4(mu2-Cp*)}]- (3), the anion exhibiting an intermetallic RhIn(3) 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*.