Computational study of the transition state for H2 addition to Vaska-type complexes (trans-Ir(L)2(CO)X)

Substituent effects on the energy barrier and the origin of the small H2/D2 kinetic isotope effect

Faraj Abu-Hasanayn, Alan S Goldman, Karsten Krogh-Jespersen

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Abstract

Ab initio molecular orbital methods have been used to study transition state properties for the concerted addition reaction of H2 to Vaska-type complexes, trans-Ir(L)2(CO)X, 1 (L = PH3 and X = F, Cl, Br, I, CN, or H; L = NH3 and X = Cl). Stationary points on the reaction path retaining the trans-L2 arrangement were located at the Hartree-Fock level using relativistic effective core potentials and valence basis sets of double-ζ quality. The identities of the stationary points were confirmed by normal mode analysis. Activation energy barriers were calculated with electron correlation effects included via Moller-Plesset perturbation theory carried fully through fourth order, MP4(SDTQ). The more reactive complexes feature structurally earlier transition states and larger reaction exothermicities, in accord with the Hammond postulate. The experimentally observed increase in reactivity of Ir(PPh3)2(CO)X complexes toward H2 addition upon going from X = F to X = I is reproduced well by the calculations and is interpreted to be a consequence of diminished halide-to-Ir π-donation by the heavier halogens. Computed activation barriers (L = PH3) range from 6.1 kcal/mol (X = H) to 21.4 kcal/mol (X = F). Replacing PH3 by NH3 when X = Cl increases the barrier from 14.1 to 19.9 kcal/mol. Using conventional transition state theory, the kinetic isotope effects for H2/D2 addition are computed to lie between 1.1 and 1.7 with larger values corresponding to earlier transition states. Judging from the computational data presented here, tunneling appears to be unimportant for H2 addition to these iridium complexes.

Original languageEnglish
Pages (from-to)5890-5896
Number of pages7
JournalJournal of Physical Chemistry
Volume97
Issue number22
Publication statusPublished - 1993

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Electron correlations
Addition reactions
Energy barriers
Iridium
Molecular orbitals
Carbon Monoxide
Isotopes
isotope effect
Activation energy
Chemical activation
Halogens
Kinetics
kinetics
energy
axioms
retaining
iridium
halogens
halides
molecular orbitals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Computational study of the transition state for H2 addition to Vaska-type complexes (trans-Ir(L)2(CO)X): Substituent effects on the energy barrier and the origin of the small H2/D2 kinetic isotope effect",
abstract = "Ab initio molecular orbital methods have been used to study transition state properties for the concerted addition reaction of H2 to Vaska-type complexes, trans-Ir(L)2(CO)X, 1 (L = PH3 and X = F, Cl, Br, I, CN, or H; L = NH3 and X = Cl). Stationary points on the reaction path retaining the trans-L2 arrangement were located at the Hartree-Fock level using relativistic effective core potentials and valence basis sets of double-ζ quality. The identities of the stationary points were confirmed by normal mode analysis. Activation energy barriers were calculated with electron correlation effects included via Moller-Plesset perturbation theory carried fully through fourth order, MP4(SDTQ). The more reactive complexes feature structurally earlier transition states and larger reaction exothermicities, in accord with the Hammond postulate. The experimentally observed increase in reactivity of Ir(PPh3)2(CO)X complexes toward H2 addition upon going from X = F to X = I is reproduced well by the calculations and is interpreted to be a consequence of diminished halide-to-Ir π-donation by the heavier halogens. Computed activation barriers (L = PH3) range from 6.1 kcal/mol (X = H) to 21.4 kcal/mol (X = F). Replacing PH3 by NH3 when X = Cl increases the barrier from 14.1 to 19.9 kcal/mol. Using conventional transition state theory, the kinetic isotope effects for H2/D2 addition are computed to lie between 1.1 and 1.7 with larger values corresponding to earlier transition states. Judging from the computational data presented here, tunneling appears to be unimportant for H2 addition to these iridium complexes.",
author = "Faraj Abu-Hasanayn and Goldman, {Alan S} and Karsten Krogh-Jespersen",
year = "1993",
language = "English",
volume = "97",
pages = "5890--5896",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "22",

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TY - JOUR

T1 - Computational study of the transition state for H2 addition to Vaska-type complexes (trans-Ir(L)2(CO)X)

T2 - Substituent effects on the energy barrier and the origin of the small H2/D2 kinetic isotope effect

AU - Abu-Hasanayn, Faraj

AU - Goldman, Alan S

AU - Krogh-Jespersen, Karsten

PY - 1993

Y1 - 1993

N2 - Ab initio molecular orbital methods have been used to study transition state properties for the concerted addition reaction of H2 to Vaska-type complexes, trans-Ir(L)2(CO)X, 1 (L = PH3 and X = F, Cl, Br, I, CN, or H; L = NH3 and X = Cl). Stationary points on the reaction path retaining the trans-L2 arrangement were located at the Hartree-Fock level using relativistic effective core potentials and valence basis sets of double-ζ quality. The identities of the stationary points were confirmed by normal mode analysis. Activation energy barriers were calculated with electron correlation effects included via Moller-Plesset perturbation theory carried fully through fourth order, MP4(SDTQ). The more reactive complexes feature structurally earlier transition states and larger reaction exothermicities, in accord with the Hammond postulate. The experimentally observed increase in reactivity of Ir(PPh3)2(CO)X complexes toward H2 addition upon going from X = F to X = I is reproduced well by the calculations and is interpreted to be a consequence of diminished halide-to-Ir π-donation by the heavier halogens. Computed activation barriers (L = PH3) range from 6.1 kcal/mol (X = H) to 21.4 kcal/mol (X = F). Replacing PH3 by NH3 when X = Cl increases the barrier from 14.1 to 19.9 kcal/mol. Using conventional transition state theory, the kinetic isotope effects for H2/D2 addition are computed to lie between 1.1 and 1.7 with larger values corresponding to earlier transition states. Judging from the computational data presented here, tunneling appears to be unimportant for H2 addition to these iridium complexes.

AB - Ab initio molecular orbital methods have been used to study transition state properties for the concerted addition reaction of H2 to Vaska-type complexes, trans-Ir(L)2(CO)X, 1 (L = PH3 and X = F, Cl, Br, I, CN, or H; L = NH3 and X = Cl). Stationary points on the reaction path retaining the trans-L2 arrangement were located at the Hartree-Fock level using relativistic effective core potentials and valence basis sets of double-ζ quality. The identities of the stationary points were confirmed by normal mode analysis. Activation energy barriers were calculated with electron correlation effects included via Moller-Plesset perturbation theory carried fully through fourth order, MP4(SDTQ). The more reactive complexes feature structurally earlier transition states and larger reaction exothermicities, in accord with the Hammond postulate. The experimentally observed increase in reactivity of Ir(PPh3)2(CO)X complexes toward H2 addition upon going from X = F to X = I is reproduced well by the calculations and is interpreted to be a consequence of diminished halide-to-Ir π-donation by the heavier halogens. Computed activation barriers (L = PH3) range from 6.1 kcal/mol (X = H) to 21.4 kcal/mol (X = F). Replacing PH3 by NH3 when X = Cl increases the barrier from 14.1 to 19.9 kcal/mol. Using conventional transition state theory, the kinetic isotope effects for H2/D2 addition are computed to lie between 1.1 and 1.7 with larger values corresponding to earlier transition states. Judging from the computational data presented here, tunneling appears to be unimportant for H2 addition to these iridium complexes.

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