TY - JOUR
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 - Publisher Copyright:
© 2023 IUPAC & De Gruyter. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. For more information, please visit: http://creativecommons.org/licenses/by-nc-nd/4.0/.
PY - 2023/3/1
Y1 - 2023/3/1
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.
KW - Activation strain model
KW - bond activation
KW - density functional calculations
KW - homogeneous catalysis
KW - oxidative addition
KW - VCCA-2022
UR - https://www.scopus.com/pages/publications/85147930967
U2 - 10.1515/pac-2022-1004
DO - 10.1515/pac-2022-1004
M3 - Article
AN - SCOPUS:85147930967
SN - 0033-4545
VL - 95
SP - 181
EP - 191
JO - Pure and Applied Chemistry
JF - Pure and Applied Chemistry
IS - 3
ER -