Oxidation of ruthenium(II) ammine complexes by 1-hydroxy-1-methylethyl radicals and by tris(bipyridyl)cobalt(III) ions
The kinetics of oxidation of Ru(NH/sub 3/)/sub 6//sup 2 +/ and of (NH/sub 3/)/sub 5/Ru(NC/sub 5/H/sub 4/X)/sup 2 +/, X = H, 3-Cl, 4-CH/sub 3/, 4-C(CH/sub 3/)/sub 3/, and 4-N(CH/sub 3/)/sub 2/, by /sup ./C(CH/sub 3/)/sub 2/OH (k/sub R/) and by Co(bpy)/sub 3//sup 3 +/ (k/sub Co/) have been evaluated. Values of log k/sub R/ vary linearly with log k/sub Co. The individual values of log k/sub R/ and log k/sub Co/ are both correlated by the Hammett sigma parameters, the reaction constants being rho = -0.50 +/- 0.03 and -1.9 +/- 0.1, respectively. The reactions of all the Ru(II) complexes with /sup ./C(CH/sub 3/)/sub 2/OH are acid-catalyzed (k/sub R/ = k/sub R0/ + k/sub R1/(H/sup +/)), an unprecedented observation. This suggests the rate-limiting step is solvolysis of an ion-paired successor complex, (RuL/sub 6//sup 3 +/,/sup -/C(CH/sub 3/)/sub 2/OH), with H/sub 2/O and H/sub 3/O/sup +/ each being solvolytically active. 30 references, 4 figures, 4 tables.
- Research Organization:
- Rudjer Boskovic Institute, Zagreb, Yugoslavia
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5796848
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:20; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
AMMINES
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
COBALT COMPOUNDS
COMPLEXES
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PYRIDINES
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS