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 ).

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.