Characterization and catalytic activity of covalently linked bipyridyl ruthenium OXO dimers

This paper reports that covalently linked bipyridyl ligands (L-L) with alkyl linkages varying from (-CH[sub 2]-)[sub 2] to (-CH[sub 2]-)[sub 12] were used to prepare ruthenium oxo dimers of the form [bpy (H[sub 2]O)RuO(L-L)Ru(H[sub 2]O) (bpy)][sup 4+]. The bridging alkyl linkage increased the stabil...

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Bibliographic Details
Published in:Journal of the Electrochemical Society 1992-08, Vol.139 (8), p.2217-2221
Main Authors: PETACH, H. H, ELLIOTT, C. M
Format: Article
Language:English
Subjects:
400400 - Electrochemistry
ALKYL RADICALS
CATALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
CLEAVAGE
COMPLEXES
COVALENCE
CRYSTAL STRUCTURE
DIMERS
ELECTROCHEMISTRY
ELECTRON SPECTROSCOPY
Exact sciences and technology
General and physical chemistry
HYDROGEN COMPOUNDS
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Kinetics and mechanism of reactions
LIGANDS
MANY-BODY PROBLEM
MICROSTRUCTURE
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PYRIDYL RADICALS
RADICALS
REFRACTORY METAL COMPOUNDS
RUTHENIUM COMPLEXES
RUTHENIUM COMPOUNDS
RUTHENIUM OXIDES
SPECTROSCOPY
STABILITY
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TWO-BODY PROBLEM
WATER
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Description
Summary:This paper reports that covalently linked bipyridyl ligands (L-L) with alkyl linkages varying from (-CH[sub 2]-)[sub 2] to (-CH[sub 2]-)[sub 12] were used to prepare ruthenium oxo dimers of the form [bpy (H[sub 2]O)RuO(L-L)Ru(H[sub 2]O) (bpy)][sup 4+]. The bridging alkyl linkage increased the stability of these oxo dimers by maintaining the relative proximity of the two ruthenium centers even when the oxo bridge is cleaved. These complexes have been characterized by electronic spectroscopy and electrochemistry. The electrochemistry in CH[sub 3]CN/0.1M TBAP exhibits a reversible one-electron oxidation followed by a second reversible two-electron oxidation which becomes catalytic in aqueous solution. The catalytic generation of dioxygen from water was observed upon bulk electrolysis of the oxo dimer at + 1.39 V.
ISSN:0013-4651
1945-7111
DOI:10.1149/1.2221205