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Water replacement on the decaaqua-di-rhodium(II) cation; synthesis of superoxo and peroxo rhodium(III) complexes with N-donor ligands

Authors
Journal
Inorganica Chimica Acta
0020-1693
Publisher
Elsevier
Publication Date
Volume
357
Issue
12
Identifiers
DOI: 10.1016/j.ica.2004.04.021
Keywords
  • Rhodium Complexes
  • Aqua Complexes
  • Superoxides
  • Peroxides

Abstract

Abstract The decaaqua-di-rhodium(II) cation has been found to be an interesting starting material in the preparation of dioxygen complexes with different N-donor ligands. Treatment of aqueous HClO 4 solution of [Rh 2(H 2O) 10] 4+ with NH 4OH/NH 3, py and/or en results in water exchange and the formation of corresponding [Rh 2 II(H 2O) 10− m (base) n (OH) m ] (4− m)+ derivatives. Reaction of the latter with dioxygen afforded superoxo and/or peroxo complexes, depending on reaction conditions: [Rh 2 III(O 2 − )(NH 3) 8(OH) 2](ClO 4) 3 ( 1), [Rh 2 III(O 2 − )(NH 3) 8(OH)(H 2O)](ClO 4) 4 ( 2), [Rh 2 III(O 2 2− )(NH 3) 10](ClO 4) 4 · 6H 2O ( 3), [Rh 2 III(O 2 − )(py) 8(H 2O) 2](ClO 4) 5 ( 4), [Rh 2 III(O 2 2− )(en) 4(H 2O) 2](ClO 4) 4 ( 5) and [Rh 2 III(O 2 − )(en) 4(H 2O) 2](ClO 4) 5 ( 6). All the obtained complexes were characterized by elemental analysis, mass spectrometry, UV–Vis, IR and ESR spectroscopies and magnetic measurements.

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