High-pressure pulse-radiolysis study of the formation and decomposition of complexes with iron-carbon σ bonds: Mechanistic comparison for different metal centers

S. Goldstein, G. Czapski, R. Van Eldik, N. Shaham, H. Cohen, D. Meyerstein

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Volumes of activation for the formation and homolysis of the transient complexes (hedta)FeIII-CO22- and (hedta)- FeIII-CH3- (HOCH2CH2N(CH2CO2-) CH2CH2N (CH2CO2-)2 = hedta) were determined using high-pressure pulse-radiolysis techniques. A comparison of the results with those for analogous complexes with other central transition-metal cations (M2+) and ligands (L) points out that (i) the reaction of MnLm with aliphatic radicals (R) proceeds via an interchange ligand substitution mechanism, i.e. MnLm + R → Lm-1Mn+1-R + L, (ii) the homolysis of the metal-carbon bonds naturally follows the same mechanism, and (iii) the volume of activation for the homolysis reaction depends strongly on the nature of the central cation, i.e. larger for Mn+1 = CrIII, CoIII, NiIII and smaller for FeIII. The volume of activation for the reaction (hedta)FeIII-CO22- + CO2•- + 2H+ → FeII(hedta)(H2O)- + CO + CO2 was measured, and the results enable a tentative proposal for the nature of the transition state of this interesting reaction.

Original languageEnglish
Pages (from-to)4966-4970
Number of pages5
JournalInorganic Chemistry
Volume40
Issue number19
DOIs
StatePublished - 10 Sep 2001

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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