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Redox-activated ligand-exchange reactions of tetrabutylammonium trans-bis(tert-butyl isocyanide) tetrahalogenoruthenate(III) complexes, [NBu4][ RuX4(CNBut)(2)](X = Cl or Br)

al Dulaimi, JP; Clark, RJH; Humphrey, DG; (2000) Redox-activated ligand-exchange reactions of tetrabutylammonium trans-bis(tert-butyl isocyanide) tetrahalogenoruthenate(III) complexes, [NBu4][ RuX4(CNBut)(2)](X = Cl or Br). Journal of the Chemical Society, Dalton Transactions (6) 933 - 939.

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Abstract

In situ IR and UV-VIS spectroelectrochemical studies have shown that reduction of the ions trans-[RuX4(CNBut)(2)](-) (X = Cl or Br) in the presence of acetonitrile or pyridine results in the formation of mer, trans-[RuX3(CNBut)(2)L](-) (L = MeCN or py), which can be oxidised reversibly to mer, trans- [RuX3(CNBut)(2)L]. The same reaction carried out in the presence of triphenylphosphine or tert-butyl isocyanide yields the disubstituted product, trans, trans, trans[ RuX2(CNBut)(2)L-2] (L = PPh3 or CNBut), which can be oxidised reversibly in each case to the isostructural monocation. Oxidation of trans-[RuX4(CNBut)(2)](-) can also be achieved, but the products are dependent upon the identity of the halide. For X = Cl the oxidation is chemically reversible at low temperature forming trans[ RuCl4(CNBut)(2)], whilst for X = Br the oxidation is irreversible and, in the presence of acetonitrile, pyridine or tert-butyl isocyanide, results in the formation of mer, trans-[RuBr3(CNBut)(2)L] (L = MeCN or py) or mer-[RuBr3(CNBut)(3)] (L = CNBut). All of the redox products have been characterised in situ by IR and UV-VIS spectroscopy in as many oxidation states as possible

Type:Article
Title:Redox-activated ligand-exchange reactions of tetrabutylammonium trans-bis(tert-butyl isocyanide) tetrahalogenoruthenate(III) complexes, [NBu4][ RuX4(CNBut)(2)](X = Cl or Br)
Additional information:Journal Article 294BP Humphrey DG Univ Coll London, Christopher Ingold Labs, 20 Gordon St, London WC1H 0AJ, England J CHEM SOC DALTON TRANS
Keywords:ACETONITRILE, As, BEHAVIOR, CHARGE-TRANSFER SPECTRA, chemistry, COMPLEX, COMPLEXES, ELECTRODE, formation, IONS, METAL-COMPLEXES, MIXED HALIDE NITRILE, MOLECULAR- STRUCTURE, OXIDATION, OXIDATION-STATES, REDUCTION, RUTHENIUM(II), SITU, spectroelectrochemical studies, spectroscopy, STATE, STATES, Temperature
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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