Oxidation of ruthenium(II) ammine complexes by 1-hydroxy-1-methylethyl radicals and by tris(bipyridyl)cobalt(III) ions

Journal Article · Wed Oct 07 00:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00267a006· OSTI ID:5796848

Bakac, A; Butkovic, V; Espenson, J H; Marcec, R; Orhanovic, M

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), Vol. 26:20
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMINES
OXIDATION
RUTHENIUM COMPLEXES
BIPYRIDINES
COBALT COMPOUNDS
EXPERIMENTAL DATA
AZINES
CHEMICAL REACTIONS
COMPLEXES
DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties