Coordination of {C₅Me₅Ir}²⁺ to [M₆O₁₉]^8– (M = Nb, Ta) – Analogies and Differences between Rh and Ir, Nb and Ta

Abstract

The reactions of [Cp*IrCl 2 ] 2 (Cp* = pentamethylcyclopentadienyl) with [M 6 O 19 ] 8-(M = Nb, Ta) anions lead to the formation of new hybrid organometallic-polyoxometalate (organometallic-POM) complexes, namely, singlecapped Na 8 [H 2 {Cp*IrNb 6 O 18 } 2 (O)]·47H 2 O (Na 8 -IrNb 12 ) and Na 6 [{Cp*Ir}Ta 6 O 19 ]·27H 2 O (Na 6 -IrTa 6 ) as well as double-capped [a] Nikolaev

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

“…Abramov and co-workers have shown molar-ratio-dependent coordination assembly of Cp*Ir−polyoxoniobate and Cp*Ir− polyoxotantalate complexes. 22 Moreover, our group found the reaction between [{(C 6 H 6 )RuCl} 2 (μ-Cl (5)�were isolated (Scheme 1), and their solid-state structures were determined using single-crystal X-ray diffraction. The coordination assembly of 1−3 in the reaction mixtures was monitored using 1 H nuclear magnetic resonance (NMR) spectroscopy.…”

Coordination capacity of Keggin anions as polytopic ligands: case study of [VNb12O40]15−

“…[9][10][11][12] In some cases grafting of organometallic fragments on the Nb and Ta hexametalates induces unexpected dimerization of the Lindqvist anions with the formation of [(M6O18)2(µ-O)] 14moieties. 10,13 The coordination also reduces the basicity of the POM and makes it more tolerant to moderately basic media thus increasing the pH window for further chemical transformations. Moreover, the enhanced solubility of hybrid group 5 based anions in MeOH is also remarkable.…”

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

“…In 2016, Abramov et al reported on the hexaniobate dimer [H 2 {Cp*Ir} 2 (Nb 6 O 18 ) 2 O] 8– and the hexatantalates [(Cp*Ir)Ta 6 O 19 ] 6– and [(Cp*Ir) 2 Ta 6 O 19 ] 4– . 15 Herein, we report on the reactivity of RhCp* and IrCp* with the heteropoly-22-tungstates [X 2 W 22 O 74 (OH) 2 ] 12– (X = Sb III and Bi III ).…”