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Ligand Effects on the Chemical Activity of Copper(I) Complexes: Outer‐ and Inner‐Sphere Oxidation of Cu I L
Author(s) -
Burg Ariela,
Maimon Eric,
Cohen Haim,
Meyerstein Dan
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600702
Subject(s) - chemistry , acetonitrile , redox , aqueous solution , reaction rate constant , inner sphere electron transfer , cyclam , copper , ligand (biochemistry) , inorganic chemistry , outer sphere electron transfer , catalysis , kinetics , electron transfer , medicinal chemistry , organic chemistry , metal , ion , biochemistry , physics , receptor , quantum mechanics
The effect of the ligands acetonitrile (AN), fumaric acid (H 2 fum) and 2,5,8,11‐tetramethyl‐2,5,8,11‐tetraazadodecane (L 1 ) on the kinetics of oxidation of Cu I complexes by [(cyclam)Ni III (SO 4 ) 2 ] – and [(NH 3 ) 5 Co III Cl] 2+ in aqueous solutions via an outer‐ and inner‐sphere mechanism, respectively, has been studied. The effects of the ligands on the electron self‐exchange rate constants have also been evaluated. All ligands studied stabilize Cu I in aqueous solution but affect the redox potential of the Cu II/I L couple differently. The ligands decrease the rate of the redox reactions and the electron self‐exchange rate constants. The results indicate that acetonitrile and alkenes should not be used as solvents for [Cu I L] + ‐catalyzed processes that involve redox steps. On the other hand, the results also suggest that [Cu I L 1 ] + should be a good catalyst for such processes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)