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

Abstract

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.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Rudjer Boskovic Institute, Zagreb, Yugoslavia
OSTI Identifier:
5796848
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 26:20
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Bakac, A, Butkovic, V, Espenson, J H, Marcec, R, and Orhanovic, M. Oxidation of ruthenium(II) ammine complexes by 1-hydroxy-1-methylethyl radicals and by tris(bipyridyl)cobalt(III) ions. United States: N. p., 1987. Web. doi:10.1021/ic00267a006.
Bakac, A, Butkovic, V, Espenson, J H, Marcec, R, & Orhanovic, M. Oxidation of ruthenium(II) ammine complexes by 1-hydroxy-1-methylethyl radicals and by tris(bipyridyl)cobalt(III) ions. United States. https://doi.org/10.1021/ic00267a006
Bakac, A, Butkovic, V, Espenson, J H, Marcec, R, and Orhanovic, M. 1987. "Oxidation of ruthenium(II) ammine complexes by 1-hydroxy-1-methylethyl radicals and by tris(bipyridyl)cobalt(III) ions". United States. https://doi.org/10.1021/ic00267a006.
@article{osti_5796848,
title = {Oxidation of ruthenium(II) ammine complexes by 1-hydroxy-1-methylethyl radicals and by tris(bipyridyl)cobalt(III) ions},
author = {Bakac, A and Butkovic, V and Espenson, J H and Marcec, R and Orhanovic, M},
abstractNote = {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.},
doi = {10.1021/ic00267a006},
url = {https://www.osti.gov/biblio/5796848}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 26:20,
place = {United States},
year = {Wed Oct 07 00:00:00 EDT 1987},
month = {Wed Oct 07 00:00:00 EDT 1987}
}