A theoretical study of the reaction H2 + Fe(CO)4 ⇌ H2Fe(CO)4

Wenhua Wang, Eric Weitz*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

44 Scopus citations

Abstract

Density functional theory (DFT) methods, with three different gradient-corrected functionals (BP86, BLYP, and B3LYP), have been used to calculate molecular geometries and energies along the pathway for oxidative addition of H2 to Fe(CO)4 leading to H2Fe(CO)4. The geometry of H2Fe(CO)4, optimized using each of the different functionals, is in good agreement with experimental results. The enthalpies for reductive elimination of H2 from H2Fe(CO)4, referenced to both the first excited singlet and the triplet ground state of Fe(CO)4, have been calculated using the BP86, BLYP, and B3LYP functionals and are compared to the experimental result of 21 ± 2 kcal mol-1. The mechanism for the oxidative addition of H2 to Fe(CO)4 is discussed and compared with experimental observations. The geometry of a dihydrogen intermediate, (η2-H2)Fe(CO)4, and the transition state between (η2-H2)Fe(CO)4 and H2Fe(CO)4, along the reaction path, has also been optimized.

Original languageEnglish (US)
Pages (from-to)2358-2363
Number of pages6
JournalJournal of Physical Chemistry A
Volume101
Issue number12
DOIs
StatePublished - Mar 20 1997

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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