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DOI: 10.1039/A702938A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 3299-3304

Redox chemistry of the [Re3(µ-Cl)3X9]3 - halides (X = Cl or Br); isolation and structural characterization of the [{Re3(µ-Cl)3Br6(H 2O)(µ-O)}2]2- cluster anion[hair space]

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Nikos Psaroudakis, Aris Terzis, Catherine P. Raptopoulou and Constantinos Mertis

Abstract

The triangulo Re39+ cluster [Re3(µ-Cl)3X9]3- (X = Cl 1a or Br 1b) in concentrated aqueous hydrohalogenic acid solutions underwent a facile one-electron reduction by various reducing agents (VCl2·4H2O, Sn–SnCl2 or Hg) to give the air-sensitive Re38+ anion [Re3(µ-Cl)3X9-n (H2O)n](4-n) - (X = Cl 2a or Br 2b), where n may be 1; the diamagnetism and EPR silence of this compound indicate that it may exist as a dimer with a direct or indirect rhenium–rhenium bond linking two Re38+ trimetal cores. Oxidation of 2 by molecular oxygen in 6 mol dm-3 HX (X = Cl or Br) solutions yielded 1 quantitatively, whereas in the absence of acid and in aprotic solvents oxo-derivatives are formed; from 2b the hexanuclear anion [{Re3(µ-Cl)3Br6(H 2O)(µ-O)}2]2- 3b was obtained whose structural characterization, as its [PPh4]+ salt 3c, shows that two µ-O ligands bridge two oxidized Re310+ units. The structure of the Re39+ cluster [Co(en)3][Re3(µ-Cl)3Br 8(H2O)]Br has been also determined by X-ray diffraction. The redox couple xRe39+–(Re38 )x, where x = 1 or 2, derived upon mixing 6 mol dm-3 HX (X = Cl or Br) solutions of 1 with an excess of mercury, catalyses efficiently the reduction of molecular oxygen to water.

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