TY - JOUR
T1 - The nature of μ3-oxohexakis(μ-acetato)triaquatriruthenium cationic complexes isolated from aqueous perchloric acid. Crystal and molecular structure of [Ru3O(O3CCH3)6(OH2)3](ClO4)·2H2O
AU - Powell, Glenmore
AU - Richens, David T.
AU - Bino, Avi
PY - 1995/4
Y1 - 1995/4
N2 - Evaporation of 2.0 M HClO4 eluates following cation-exchange chromatography of aqueous solutions of [Ru3O(O2CCH3)6(OH2)3](O2CCH3) has allowed crystallisation and structural characterisation of the complex [Ru3O(O2CCH3)6(OH2)3](ClO4)·2H2O. A blue-green to purple colour change occurs in the mother liquor during the crystallisation process indicative of accompanying oxidation in solution to the purple dicationic Ru(III,III,IV) complex. Elution with more dilute (0.2 M) HClO4 solutions allows only isolation of the Ru(III,III,IV) complex due to a higher solubility and resulting oxidation by ClO4- ions prior to crystallisation. The structural analysis of [Ru3O(O2CCH3)6(OH2)3](ClO4)·2H2O provides further support for the non-bonded character of the orbitals involved with electron transfer between the Ru(III,III,III) and Ru(III,III,IV) forms of these complexes. Individual RuRu and RuO distances indicate that in the Ru(III,III,IV) complex the Ru centres are valence delocalised at room temperature.
AB - Evaporation of 2.0 M HClO4 eluates following cation-exchange chromatography of aqueous solutions of [Ru3O(O2CCH3)6(OH2)3](O2CCH3) has allowed crystallisation and structural characterisation of the complex [Ru3O(O2CCH3)6(OH2)3](ClO4)·2H2O. A blue-green to purple colour change occurs in the mother liquor during the crystallisation process indicative of accompanying oxidation in solution to the purple dicationic Ru(III,III,IV) complex. Elution with more dilute (0.2 M) HClO4 solutions allows only isolation of the Ru(III,III,IV) complex due to a higher solubility and resulting oxidation by ClO4- ions prior to crystallisation. The structural analysis of [Ru3O(O2CCH3)6(OH2)3](ClO4)·2H2O provides further support for the non-bonded character of the orbitals involved with electron transfer between the Ru(III,III,III) and Ru(III,III,IV) forms of these complexes. Individual RuRu and RuO distances indicate that in the Ru(III,III,IV) complex the Ru centres are valence delocalised at room temperature.
KW - Aqua complexes
KW - Carboxylate complexes
KW - Crystal structures
KW - Oxo complexes
KW - Ruthenium complexes
UR - http://www.scopus.com/inward/record.url?scp=0001146112&partnerID=8YFLogxK
U2 - 10.1016/0020-1693(94)04396-D
DO - 10.1016/0020-1693(94)04396-D
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AN - SCOPUS:0001146112
SN - 0020-1693
VL - 232
SP - 167
EP - 170
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1-2
ER -