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On the Mechanism of the Palladium Bis(NHC) Complex Catalyzed CH Functionalization of Propane: Experiment and DFT Calculations
Author(s) -
Munz Dominik,
Strassner Thomas
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201403910
Subject(s) - palladium , catalysis , regioselectivity , steric effects , chemistry , surface modification , carbene , halide , propane , kinetic isotope effect , combinatorial chemistry , computational chemistry , mechanism (biology) , chelation , electronic effect , organic chemistry , philosophy , physics , deuterium , quantum mechanics , epistemology
We report a detailed mechanistic study on the CH functionalization of alkanes by palladium complexes with chelating bis( N ‐heterocyclic carbene) (NHC) complexes. The experimental results are complemented by detailed DFT calculations, which allow us to rationalize the regioselectivity and the catalytic activity. The study includes a library of catalysts with different electronic and steric properties, kinetic data, and isotope effects. The combined experimental and computational results favor a mechanism involving organometallic palladium(IV) intermediates. Furthermore, it is shown that at high halide loadings a different mechanism is operative.