Organorhodium(III)- and Iridium(III)-Substituted 20-Tungstobismuthates(III) and -Antimonates(III), [(MCp*)2X2W20O70]10- (M = RhIII and IrIII; X = BiIII and SbIII).

The synthesis of four organometallic RhCp*- and IrCp*-containing heteropoly-20-tungstates, [{RhCp*}2Bi2W20O70]10- (1), [{IrCp*}2Bi2W20O70]10- (2), [{RhCp*}2Sb2W20O70]10- (3), and [{IrCp*}2Sb2W20O70]10- (4) has been accomplished by reaction of (MCp*Cl2)2 with [X2W22O74(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 183W and 13C NMR. For the Rh derivatives 1 and 3 the 183W-103Rh coupling (2 J W-Rh 3.0 Hz) could be identified by 183W NMR.