Theoretical Studies of Oxidative Addition and Reductive Elimination: H2 + Pt(PH3)2 → Pt(H)2(PH3)2

John J. Low; William A. Goddard

doi:10.1021/ja00335a010

Theoretical Studies of Oxidative Addition and Reductive Elimination: H₂ + Pt(PH₃)₂ → Pt(H)₂(PH₃)₂

John J. Low
, William A. Goddard

California Institute of Technology

Résultats de recherche: Contribution à un journal › Article › Revue par des pairs

Résumé

Ab initio calculations (Hartree-Fock, generalized valence bond, and configuration interaction), utilizing relativistic core potentials, have been used to follow the oxidative addition of H₂ to Pt(PH₃)₂. We find an activation barrier of 2.3 kcal/mol and an exothermicity of 15.9 kcal/mol. From examination of the geometries and wave functions, we find that up to the transition state the H-H bond is still intact. The role of the Pt s¹d⁹ and d¹⁰ states in oxidative addition is described, and the effects of including electronic correlation are discussed. The implications for reductive elimination of the dimethyl and hydridomethyl complexes are also discussed.

langue originale	Anglais
Pages (de - à)	6928-6937
Nombre de pages	10
journal	Journal of the American Chemical Society
Volume	106
Numéro de publication	23
Les DOIs	https://doi.org/10.1021/ja00335a010
état	Publié - 1 janv. 1984
Modification externe	Oui

Accès au document

10.1021/ja00335a010

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title = "Theoretical Studies of Oxidative Addition and Reductive Elimination: H2 + Pt(PH3)2 → Pt(H)2(PH3)2",

abstract = "Ab initio calculations (Hartree-Fock, generalized valence bond, and configuration interaction), utilizing relativistic core potentials, have been used to follow the oxidative addition of H2 to Pt(PH3)2. We find an activation barrier of 2.3 kcal/mol and an exothermicity of 15.9 kcal/mol. From examination of the geometries and wave functions, we find that up to the transition state the H-H bond is still intact. The role of the Pt s1d9 and d10 states in oxidative addition is described, and the effects of including electronic correlation are discussed. The implications for reductive elimination of the dimethyl and hydridomethyl complexes are also discussed.",

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AU - Goddard, William A.

PY - 1984/1/1

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N2 - Ab initio calculations (Hartree-Fock, generalized valence bond, and configuration interaction), utilizing relativistic core potentials, have been used to follow the oxidative addition of H2 to Pt(PH3)2. We find an activation barrier of 2.3 kcal/mol and an exothermicity of 15.9 kcal/mol. From examination of the geometries and wave functions, we find that up to the transition state the H-H bond is still intact. The role of the Pt s1d9 and d10 states in oxidative addition is described, and the effects of including electronic correlation are discussed. The implications for reductive elimination of the dimethyl and hydridomethyl complexes are also discussed.

AB - Ab initio calculations (Hartree-Fock, generalized valence bond, and configuration interaction), utilizing relativistic core potentials, have been used to follow the oxidative addition of H2 to Pt(PH3)2. We find an activation barrier of 2.3 kcal/mol and an exothermicity of 15.9 kcal/mol. From examination of the geometries and wave functions, we find that up to the transition state the H-H bond is still intact. The role of the Pt s1d9 and d10 states in oxidative addition is described, and the effects of including electronic correlation are discussed. The implications for reductive elimination of the dimethyl and hydridomethyl complexes are also discussed.

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