TY - JOUR
T1 - A theoretical study of the reaction H2 + Fe(CO)4 ⇌ H2Fe(CO)4
AU - Wang, Wenhua
AU - Weitz, Eric
PY - 1997/3/20
Y1 - 1997/3/20
N2 - 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.
AB - 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.
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U2 - 10.1021/jp964090z
DO - 10.1021/jp964090z
M3 - Article
AN - SCOPUS:0000427547
VL - 101
SP - 2358
EP - 2363
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 12
ER -