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 (2JW‑Rh 3.0 Hz) could be identified by 183W NMR.

本研究通过(MCp*Cl₂)₂与[X₂W₂₂O₇₄(OH)₂]¹²⁻在pH为6的水溶液中、70℃条件下发生反应，成功合成了四种含有机金属RhCp*与IrCp*的杂多20钨酸盐：[{RhCp*}₂Bi₂W₂₀O₇₀]¹⁰⁻（1）、[{IrCp*}₂Bi₂W₂₀O₇₀]¹⁰⁻（2）、[{RhCp*}₂Sb₂W₂₀O₇₀]¹⁰⁻（3）以及[{IrCp*}₂Sb₂W₂₀O₇₀]¹⁰⁻（4）。上述四种多阴离子1~4的结构已分别通过单晶X射线衍射（single-crystal XRD）、傅里叶变换红外光谱（FTIR）与热重分析（TGA）在固态下完成表征，并通过钨-183（¹⁸³W）与碳-13（¹³C）核磁共振（NMR）在溶液中完成结构表征。针对其中的铑衍生物1和3，可通过¹⁸³W核磁共振谱观测到其¹⁸³W与¹⁰³Rh之间的自旋耦合作用，耦合常数为2J_W-Rh=3.0 Hz。