H2 Binding, Splitting, and Net Hydrogen Atom Transfer at a Paramagnetic Iron Complex

Demyan E. Prokopchuk, Geoffrey M. Chambers, Eric D. Walter, Michael T. Mock, R. Morris Bullock

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

While diamagnetic transition metal complexes that bind and split H2 have been extensively studied, paramagnetic complexes that exhibit this behavior remain rare. The square planar S = 1/2 FeI(P4N2)+ cation (FeI+) reversibly binds H2/D2 in solution, exhibiting an inverse equilibrium isotope effect of KH2/KD2 = 0.58(4) at -5.0 °C. In the presence of excess H2, the dihydrogen complex FeI(H2)+ cleaves H2 at 25 °C in a net hydrogen atom transfer reaction, producing the dihydrogen-hydride trans-FeII(H)(H2)+. The proposed mechanism of H2 splitting involves both intra- and intermolecular steps, resulting in a mixed first- and second-order rate law with respect to initial [FeI+]. The key intermediate is a paramagnetic dihydride complex, trans-FeIII(H)2+, whose weak FeIII-H bond dissociation free energy (calculated BDFE = 44 kcal/mol) leads to bimetallic H-H homolysis, generating trans-FeII(H)(H2)+. Reaction kinetics, thermodynamics, electrochemistry, EPR spectroscopy, and DFT calculations support the proposed mechanism.

Original languageEnglish
Pages (from-to)1871-1876
Number of pages6
JournalJournal of the American Chemical Society
Volume141
Issue number5
DOIs
Publication statusPublished - Feb 6 2019

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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