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)

Abstract

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.

Self-assembly of a unique triangle-like tungstovanadate containing pentagonal {(WO7)W3(SnR)2} cluster

“…have been successfully synthesized under certain conditions. [13][14][15][16] Organotins generally refer to alkyltin, estertin or carboxyltin compounds. Estertin or carboxyltin compounds have good thermal stability and are commonly used as thermal stabilizers.…”

Molar-Ratio-Dependent Coordination Assembly of Organoiridium(III)-Octatungstate Complexes in Aqueous Solution

“…We are particularly interested in organoiridium(III)containing polyoxotungstates 6,18 because they are relevant to water-oxidation catalysts based on the Ir/WO 3 system. 19,20 Most known organoiridium(III)−polyoxotungstates contain {Cp*Ir} 2+ (Cp* is pentamethylcyclopentadienyl anion, C 5 (CH 3 ) 5 − ) fragments; their structures and synthetic conditions are summarized in Table S1.…”

“…We are particularly interested in organoiridium­(III)-containing polyoxotungstates , because they are relevant to water-oxidation catalysts based on the Ir/WO 3 system. , Most known organoiridium­(III)–polyoxotungstates contain {Cp*Ir} 2+ (Cp* is pentamethylcyclopentadienyl anion, C 5 (CH 3 ) 5 – ) fragments; their structures and synthetic conditions are summarized in Table S1. Niu and co-workers reported the first example of a Cp*Ir–polyoxotungstate complex formulated as H 4 [(Cp*Ir) 4 W 8 O 32 ]·17.33H 2 O which was prepared by the reaction between [(Cp*IrCl) 2 (μ-Cl) 2 ] and Na 2 WO 4 in a 1:4 molar ratio in water .…”