One electron organozinc ligands in metal rich molecules by Ga/Zn exchange: from Cp*Rh(GaCp*)2 to Cp*Rh(ZnR)4 units.

Two unusual compounds, [{Cp*Rh(ZnCp*)(2)(ZnMe)(ZnCl)}(2)] (1) and [Cp*(2)Rh][(Cp*Rh)(6)Zn(18)Cl(12)(mu(6)-Cl)] (2), both bearing closed shell 18-electron square pyramidal Cp*RhZn(4) building units were obtained by combined Ga/Zn, Me/Cp* and Me/Cl exchange upon treatment of [Cp*Rh(GaCp*)(2)(GaCl(2)Cp*)] with ZnMe(2) (Cp* = pentamethylcyclopentadienyl).