Ligand effects on the chemical activity of copper(I) complexes: Outer- and inner-sphere oxidation of CuIL

Ariela Burg, Eric Maimon, Haim Cohen, Dan Meyerstein

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The effect of the ligands acetonitrile (AN), fumaric acid (H 2fum) and 2,5,8,11-tetramethyl-2,5,8,11-tetraazadodecane (L 1) on the kinetics of oxidation of CuI complexes by [(cy-clam)NiIII(SO4)2] and [(NH 3)5CoIIIC1]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 CuI in aqueous solution but affect the redox potential of the CuII/IL 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 [CuIL]+-catalyzed processes that involve redox steps. On the other hand, the results also suggest that [CuIL1]+ should be a good catalyst for such processes.

Original languageEnglish
Pages (from-to)530-536
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Issue number4
DOIs
StatePublished - 2007
Externally publishedYes

Keywords

  • Copper
  • Electron self exchange rate constant
  • Inner-sphere mechanism
  • Outer-sphere mechanism

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