Organorhodium(III)- and Iridium(III)-Substituted 20-Tungstobismuthates(III) and -Antimonates(III), [(MCp*)₂X₂W₂₀O₇₀]^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*}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 (2JW‑Rh 3.0 Hz) could be identified by 183W NMR.