Hammett correlations as test of mechanism of CO-induced disulfide elimination from dinitrosyl iron complexes Academic Article uri icon


  • The displacement of RS from [(NHC)(SPh)Fe(NO)2] (NHC = N-heterocyclic carbene) by carbon monoxide follows associative kinetics, rate = k [CO]1 [(NHC)(SPh)Fe(NO)2]1, resulting in reduction of the oxidized form of the dinitrosyliron unit, {Fe(NO) 2}9 (Enemark-Feltham notation) to {Fe(NO) 2}10. Thermodynamically driven by the release of PhS-SPh concomitant with formation of [(NHC)(CO)Fe(NO)2], computational studies suggested the reactant dinitrosyliron unit serves as a nucleophile in the initial slanted interaction of the π* orbital of CO, shifting into normal linear Fe-CO with weakening of the Fe-SPh bond. The current study seeks to experimentally test this proposal. A series of analogous {Fe(NO) 2}9 [(NHC)(p-S-C6H4X)Fe(NO) 2] complexes, with systematic variation of the para-substituents X from electron donor to electron withdrawing groups was used to monitor variation in electron density at the Fe(NO)2 unit via Hammett analyses. Despite the presence of non-innocent NO ligands, data from ν(NO) IR spectroscopy and cyclic voltammetry showed consistent tracking of the electron density at the {Fe(NO)2} unit in response to the aryl substituent. The electronic modifications resulted in systematic changes in reaction rates when each derivative was exposed to CO. A plot of the rate constants and the Hammett parameter σp is linear with a negative slope and a ρ value of -0.831; such correlation is indicative of rate retardation by electron-withdrawing substituents, and provides experimental support for the unique role of the delocalized frontier molecular orbitals of the Fe(NO) 2 unit. © 2014 the Partner Organisations.

altmetric score

  • 1

author list (cited authors)

  • Pulukkody, R., Kyran, S. J., Drummond, M. J., Hsieh, C., Darensbourg, D. J., & Darensbourg, M. Y.

citation count

  • 7

publication date

  • January 2014