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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?

SUBMITTER: Vermeeren P

PROVIDER: S-EPMC6048108 | biostudies-other | 2018 Jul

REPOSITORIES: biostudies-other

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

Vermeeren Pascal P Sun Xiaobo X Bickelhaupt F Matthias FM

Scientific reports 20180716 1

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 ...[more]

PMID: 30013049

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