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 E¹Cp* (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 E¹Cp* (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*₂Rh]⁺[Cp*Rh(InCp*){In ₂Cl₄(μ₂-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*)(C₂H ₄)}₂] (7) can be prepared by treatment of [RhCp*(CH₃CN)(C₂H₄)] with GaCp*.