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 explo...

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Main Authors:	Pascal Vermeeren, Xiaobo Sun, F. Matthias Bickelhaupt
Format:	article
Language:	EN
Published:	Nature Portfolio 2018
Subjects:	Medicine R Science Q
Online Access:	https://doaj.org/article/ceabaa0dbacf4233933abfd0fa8fabda
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spelling	oai:doaj.org-article:ceabaa0dbacf4233933abfd0fa8fabda2021-12-02T12:31:56ZArylic C–X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends10.1038/s41598-018-28998-32045-2322https://doaj.org/article/ceabaa0dbacf4233933abfd0fa8fabda2018-07-01T00:00:00Zhttps://doi.org/10.1038/s41598-018-28998-3https://doaj.org/toc/2045-2322Abstract 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.Pascal VermeerenXiaobo SunF. Matthias BickelhauptNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 8, Iss 1, Pp 1-10 (2018)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Pascal Vermeeren Xiaobo Sun F. Matthias Bickelhaupt Arylic C–X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends
description	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.
format	article
author	Pascal Vermeeren Xiaobo Sun F. Matthias Bickelhaupt
author_facet	Pascal Vermeeren Xiaobo Sun F. Matthias Bickelhaupt
author_sort	Pascal Vermeeren
title	Arylic C–X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends
title_short	Arylic C–X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends
title_full	Arylic C–X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends
title_fullStr	Arylic C–X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends
title_full_unstemmed	Arylic C–X Bond Activation by Palladium Catalysts: Activation Strain Analyses of Reactivity Trends
title_sort	arylic c–x bond activation by palladium catalysts: activation strain analyses of reactivity trends
publisher	Nature Portfolio
publishDate	2018
url	https://doaj.org/article/ceabaa0dbacf4233933abfd0fa8fabda
work_keys_str_mv	AT pascalvermeeren aryliccxbondactivationbypalladiumcatalystsactivationstrainanalysesofreactivitytrends AT xiaobosun aryliccxbondactivationbypalladiumcatalystsactivationstrainanalysesofreactivitytrends AT fmatthiasbickelhaupt aryliccxbondactivationbypalladiumcatalystsactivationstrainanalysesofreactivitytrends
_version_	1718394244083744768

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

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