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

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	6928-6937
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	106
Issue number	23
DOIs	https://doi.org/10.1021/ja00335a010
Publication status	Published - 1 Jan 1984
Externally published	Yes

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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.",

author = "Low, \{John J.\} and Goddard, \{William A.\}",

year = "1984",

month = jan,

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doi = "10.1021/ja00335a010",

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T2 - H2 + Pt(PH3)2 → Pt(H)2(PH3)2

AU - Low, John J.

AU - Goddard, William A.

PY - 1984/1/1

Y1 - 1984/1/1

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.

UR - https://www.scopus.com/pages/publications/33845469680

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DO - 10.1021/ja00335a010

M3 - Article

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SN - 0002-7863

VL - 106

SP - 6928

EP - 6937

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

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

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