Arylic C-X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends

Pascal Vermeeren; Xiaobo Sun; F. Matthias Bickelhaupt

doi:10.1038/s41598-018-28998-3

Arylic C-X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends

Pascal Vermeeren, Xiaobo Sun, F. Matthias Bickelhaupt^*

^*Corresponding author for this work

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

Abstract

We have quantum chemically explored arylic carbon-substituent bond activation via oxidative insertion of a palladium catalyst in C₆H₅X + PdL_n model systems (X = H, Cl, CH₃; L_n = no ligand, PH₃, (PH₃)₂, PH₂C₂H₄PH₂) using relativistic density functional theory at ZORA-BLYP/TZ2P. Besides exploring reactivity trends and comparing them to aliphatic C-X activation, we aim at uncovering the physical factors behind the activity and selectivity. Our results show that barriers for arylic C-X activation are lower than those for the corresponding aliphatic C-X bonds. However, trends along bonds or upon variation of ligands are similar. Thus, bond activation barriers increase along C-Cl < C-H < C-C and along Pd < Pd(PH₃) or Pd(PH₂C₂H₄PH₂) < Pd(PH₃)₂. Activation strain analyses in conjunction with quantitative molecular orbital theory trace these trends to the rigidity and bonding capability of the various C-X bonds, model catalysts, and ligands.

Original language	English
Article number	10729
Pages (from-to)	1-10
Number of pages	10
Journal	Scientific Reports
Volume	8
DOIs	https://doi.org/10.1038/s41598-018-28998-3
Publication status	Published - 16 Jul 2018

Funding

We thank the Netherlands Organization for Scientific Research (NWO), the Dutch Astrochemistry Network (DAN), and the China Scholarship Council (CSC) for financial support.

Funders	Funder number
Dutch Astrochemistry Network
Netherlands Organization for Scientific Research
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
China Scholarship Council

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title = "Arylic C-X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends",

abstract = "We have quantum chemically explored arylic carbon-substituent bond activation via oxidative insertion of a palladium catalyst in C6H5X + PdLn model systems (X = H, Cl, CH3; Ln = no ligand, PH3, (PH3)2, PH2C2H4PH2) using relativistic density functional theory at ZORA-BLYP/TZ2P. Besides exploring reactivity trends and comparing them to aliphatic C-X activation, we aim at uncovering the physical factors behind the activity and selectivity. Our results show that barriers for arylic C-X activation are lower than those for the corresponding aliphatic C-X bonds. However, trends along bonds or upon variation of ligands are similar. Thus, bond activation barriers increase along C-Cl < C-H < C-C and along Pd < Pd(PH3) or Pd(PH2C2H4PH2) < Pd(PH3)2. Activation strain analyses in conjunction with quantitative molecular orbital theory trace these trends to the rigidity and bonding capability of the various C-X bonds, model catalysts, and ligands.",

author = "Pascal Vermeeren and Xiaobo Sun and Bickelhaupt, {F. Matthias}",

year = "2018",

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T2 - Activation Strain Analyses of Reactivity Trends

AU - Vermeeren, Pascal

AU - Sun, Xiaobo

AU - Bickelhaupt, F. Matthias

PY - 2018/7/16

Y1 - 2018/7/16

N2 - We have quantum chemically explored arylic carbon-substituent bond activation via oxidative insertion of a palladium catalyst in C6H5X + PdLn model systems (X = H, Cl, CH3; Ln = no ligand, PH3, (PH3)2, PH2C2H4PH2) using relativistic density functional theory at ZORA-BLYP/TZ2P. Besides exploring reactivity trends and comparing them to aliphatic C-X activation, we aim at uncovering the physical factors behind the activity and selectivity. Our results show that barriers for arylic C-X activation are lower than those for the corresponding aliphatic C-X bonds. However, trends along bonds or upon variation of ligands are similar. Thus, bond activation barriers increase along C-Cl < C-H < C-C and along Pd < Pd(PH3) or Pd(PH2C2H4PH2) < Pd(PH3)2. Activation strain analyses in conjunction with quantitative molecular orbital theory trace these trends to the rigidity and bonding capability of the various C-X bonds, model catalysts, and ligands.

AB - We have quantum chemically explored arylic carbon-substituent bond activation via oxidative insertion of a palladium catalyst in C6H5X + PdLn model systems (X = H, Cl, CH3; Ln = no ligand, PH3, (PH3)2, PH2C2H4PH2) using relativistic density functional theory at ZORA-BLYP/TZ2P. Besides exploring reactivity trends and comparing them to aliphatic C-X activation, we aim at uncovering the physical factors behind the activity and selectivity. Our results show that barriers for arylic C-X activation are lower than those for the corresponding aliphatic C-X bonds. However, trends along bonds or upon variation of ligands are similar. Thus, bond activation barriers increase along C-Cl < C-H < C-C and along Pd < Pd(PH3) or Pd(PH2C2H4PH2) < Pd(PH3)2. Activation strain analyses in conjunction with quantitative molecular orbital theory trace these trends to the rigidity and bonding capability of the various C-X bonds, model catalysts, and ligands.

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Arylic C-X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends

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