Palladium-catalyzed activation of HnA-AHnbonds (AHn= CH3, NH2, OH, F)

Bryan Phuti Moloto; Pascal Vermeeren; Marco Dalla Tiezza; Tessel Bouwens; Catharine Esterhuysen; Trevor A. Hamlin; F. Matthias Bickelhaupt

doi:10.1515/pac-2022-1004

Palladium-catalyzed activation of H_nA-AH_nbonds (AH_n= CH₃, NH₂, OH, F)

Bryan Phuti Moloto, Pascal Vermeeren, Marco Dalla Tiezza, Tessel Bouwens, Catharine Esterhuysen, Trevor A. Hamlin^*, F. Matthias Bickelhaupt

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

We have quantum chemically studied activation of HnA-AHn bonds (AHn = CH3, NH2, OH, F) by PdLn catalysts with Ln = no ligand, PH3, (PH3)2, using relativistic density functional theory at ZORA-BLYP/TZ2P. The activation energy associated with the oxidative addition step decreases from H3C-CH3 to H2N-NH2 to HO-OH to F-F, where the activation of the F-F bond is barrierless. Activation strain and Kohn-Sham molecular orbital analyses reveal that the enhanced reactivity along this series of substrates originates from a combination of (i) reduced activation strain due to a weaker HnA-AHn bond; (ii) decreased Pauli repulsion as a result of a difference in steric shielding of the HnA-AHn bond; and (iii) enhanced backbonding interaction between the occupied 4d atomic orbitals of the palladium catalyst and σ∗ acceptor orbital of the substrate.

Original language	English
Pages (from-to)	181-191
Number of pages	11
Journal	Pure and Applied Chemistry
Volume	95
Issue number	3
Early online date	2 Feb 2023
DOIs	https://doi.org/10.1515/pac-2022-1004
Publication status	Published - 28 Mar 2023

Bibliographical note

Funding Information:
We thank the National Research Foundation of South Africa (NRF, UID grant no. 115979 and CPRR grant no. 141992), Nuffic’s Netherlands Education Support Office (NESO), and Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e-infrastructure with the support of SURF cooperative.

Publisher Copyright:
© 2023 IUPAC & De Gruyter.

Funding

We thank the National Research Foundation of South Africa (NRF, UID grant no. 115979 and CPRR grant no. 141992), Nuffic’s Netherlands Education Support Office (NESO), and Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e-infrastructure with the support of SURF cooperative.

Keywords

Activation strain model
bond activation
density functional calculations
homogeneous catalysis
oxidative addition
VCCA-2022

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1515/pac-2022-1004

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Cite this

@article{55e90de30b43402b96b67c5eebca75e9,

title = "Palladium-catalyzed activation of HnA-AHnbonds (AHn= CH3, NH2, OH, F)",

abstract = "We have quantum chemically studied activation of HnA-AHn bonds (AHn = CH3, NH2, OH, F) by PdLn catalysts with Ln = no ligand, PH3, (PH3)2, using relativistic density functional theory at ZORA-BLYP/TZ2P. The activation energy associated with the oxidative addition step decreases from H3C-CH3 to H2N-NH2 to HO-OH to F-F, where the activation of the F-F bond is barrierless. Activation strain and Kohn-Sham molecular orbital analyses reveal that the enhanced reactivity along this series of substrates originates from a combination of (i) reduced activation strain due to a weaker HnA-AHn bond; (ii) decreased Pauli repulsion as a result of a difference in steric shielding of the HnA-AHn bond; and (iii) enhanced backbonding interaction between the occupied 4d atomic orbitals of the palladium catalyst and σ∗ acceptor orbital of the substrate.",

keywords = "Activation strain model, bond activation, density functional calculations, homogeneous catalysis, oxidative addition, VCCA-2022",

author = "Moloto, {Bryan Phuti} and Pascal Vermeeren and Tiezza, {Marco Dalla} and Tessel Bouwens and Catharine Esterhuysen and Hamlin, {Trevor A.} and Bickelhaupt, {F. Matthias}",

note = "Funding Information: We thank the National Research Foundation of South Africa (NRF, UID grant no. 115979 and CPRR grant no. 141992), Nuffic{\textquoteright}s Netherlands Education Support Office (NESO), and Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e-infrastructure with the support of SURF cooperative. Publisher Copyright: {\textcopyright} 2023 IUPAC & De Gruyter.",

year = "2023",

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doi = "10.1515/pac-2022-1004",

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T1 - Palladium-catalyzed activation of HnA-AHnbonds (AHn= CH3, NH2, OH, F)

AU - Moloto, Bryan Phuti

AU - Vermeeren, Pascal

AU - Tiezza, Marco Dalla

AU - Bouwens, Tessel

AU - Esterhuysen, Catharine

AU - Hamlin, Trevor A.

AU - Bickelhaupt, F. Matthias

N1 - Funding Information: We thank the National Research Foundation of South Africa (NRF, UID grant no. 115979 and CPRR grant no. 141992), Nuffic’s Netherlands Education Support Office (NESO), and Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e-infrastructure with the support of SURF cooperative. Publisher Copyright: © 2023 IUPAC & De Gruyter.

PY - 2023/3/28

Y1 - 2023/3/28

N2 - We have quantum chemically studied activation of HnA-AHn bonds (AHn = CH3, NH2, OH, F) by PdLn catalysts with Ln = no ligand, PH3, (PH3)2, using relativistic density functional theory at ZORA-BLYP/TZ2P. The activation energy associated with the oxidative addition step decreases from H3C-CH3 to H2N-NH2 to HO-OH to F-F, where the activation of the F-F bond is barrierless. Activation strain and Kohn-Sham molecular orbital analyses reveal that the enhanced reactivity along this series of substrates originates from a combination of (i) reduced activation strain due to a weaker HnA-AHn bond; (ii) decreased Pauli repulsion as a result of a difference in steric shielding of the HnA-AHn bond; and (iii) enhanced backbonding interaction between the occupied 4d atomic orbitals of the palladium catalyst and σ∗ acceptor orbital of the substrate.

AB - We have quantum chemically studied activation of HnA-AHn bonds (AHn = CH3, NH2, OH, F) by PdLn catalysts with Ln = no ligand, PH3, (PH3)2, using relativistic density functional theory at ZORA-BLYP/TZ2P. The activation energy associated with the oxidative addition step decreases from H3C-CH3 to H2N-NH2 to HO-OH to F-F, where the activation of the F-F bond is barrierless. Activation strain and Kohn-Sham molecular orbital analyses reveal that the enhanced reactivity along this series of substrates originates from a combination of (i) reduced activation strain due to a weaker HnA-AHn bond; (ii) decreased Pauli repulsion as a result of a difference in steric shielding of the HnA-AHn bond; and (iii) enhanced backbonding interaction between the occupied 4d atomic orbitals of the palladium catalyst and σ∗ acceptor orbital of the substrate.

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