Oxidation of cobalt(II) macrocycles by tris(bipyridyl)ruthenium(III) ions

Autor:	Andreja Bakac, Shaoyung Lee, James H. Espenson
Rok vydání:	1990
Předmět:	Degree (graph theory) Chemistry Inorganic chemistry chemistry.chemical_element Ruthenium Marcus theory Inorganic Chemistry Chemical kinetics Electron transfer Crystallography Reaction rate constant Flash photolysis Physical and Theoretical Chemistry Cobalt
Zdroj:	Inorganic Chemistry. 29:2480-2482
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic00338a018
Popis:	The kinetics of the electron-transfer reactions between Ru(bpy){sub 3}{sup 3+} and selected Co(II) complexes were evaluated by laser flash photolysis. The cobalt(II) complexes investigated were (H{sub 2}O){sub 2}Co(N{sub 4}mac){sup 2+}, with N{sub 4}mac = (14)aneN{sub 4}, C-meso-Me{sub 6}(14)aneN{sub 4}, tim ((14)tetraeneN{sub 4}), (15)aneN{sub 4}, and tmc (1,4,8,11-tetramethylcyclam). The respective second-order rate constants at 25{degree}C, {mu} = 0.10 M, are 3.2 {times} 10{sup 7}, 7.8 {times} 10{sup 6}, 2.1 {times} 10{sup 7}, 1.7 {times} 10{sup 7}, and 6 {times} 10{sup 5} M{sup {minus}1} s{sup {minus}1}. The results have been evaluated for their agreement with the Marcus theory. The complex Co(tmc){sup 2+} also reacts with Ru(phen){sub 3}{sup 3+} (k = 1.0 {times} 10{sup 6} M{sup {minus}1} s{sup {minus}1}) and with Ru(4,7-Me{sub 2}phen){sub 3}{sup 3+} (k = 3.2 {times} 10{sup 4} M{sup {minus}1} s{sup {minus}1}). These cobalt(II) complexes also quench the emission of the excited-state complex {sup *}Cr(bpy){sub 3}{sup 3+}. Quenching occurs by electron transfer, except for Co(tmc){sup 2+}, which appears to react by energy transfer. 41 refs., 2 figs., 1 tab.
Databáze:	OpenAIRE
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