Organorhodium(III)- and Iridium(III)-Substituted 20-Tungstobismuthates(III) and -Antimonates(III), [(MCp*)(2)X(2)W(20)O(70)](10–) (M = Rh(III) and Ir(III); X = Bi(III) and Sb(III))

[Image: see text] The synthesis of four organometallic RhCp*- and IrCp*-containing heteropoly-20-tungstates, [{RhCp*}(2)Bi(2)W(20)O(70)](10–) (1), [{IrCp*}(2)Bi(2)W(20)O(70)](10–) (2), [{RhCp*}(2)Sb(2)W(20)O(70)](10–) (3), and [{IrCp*}(2)Sb(2)W(20)O(70)](10–) (4) has been accomplished by reaction of (MCp*Cl(2))(2) with [X(2)W(22)O(74)(OH)(2)](12–) in aqueous solution at pH 6 and 70 °C. The four polyanions 1–4 were structurally characterized in the solid state by single-crystal XRD, FTIR, and TGA and in solution by (183)W and (13)C NMR. For the Rh derivatives 1 and 3 the (183)W–(103)Rh coupling ((2)J(W-Rh) 3.0 Hz) could be identified by (183)W NMR.