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Understanding the Role of Solvents and Spin–Orbit Coupling in an Oxygen‐Assisted S N 2‐Type Oxidative Transmetalation Reaction
Author(s) -
Ghosh Boyli,
Banerjee Ambar,
Paul Ankan
Publication year - 2019
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.201903281
Subject(s) - transmetalation , chemistry , oxygen , singlet oxygen , photochemistry , solvent , complete active space , computational chemistry , oxidative coupling of methane , catalysis , chemical physics , density functional theory , basis set , organic chemistry
Abstract The aerial oxidation of Pd II to Pd IV has emerged as an integral component of sustainable catalytic C−H functionalization processes. However, a proper understanding of the factors that control the viability of this oxidative process remains elusive. An investigation of the intricate mechanism of the transmetalation reaction of the aerial oxidative transformation of [(Me 3 tacn)Pd II Me 2 ] (Me 3 tacn= N , N ′, N ′′‐trimethyl‐1,4,7‐triazacyclononane) to [(Me 3 tacn)Pd IV Me 3 ] + has been conducted by using DFT, along with multireference methods, such as second‐order n ‐electron valence‐state perturbation theory (NEVPT2) with complete active space self‐consistent field theory (CASSCF). The present endeavor predicts that the thermodynamics and kinetics of the oxygen activation step are primarily dictated by the polarity of the solvents, which determine the amount of charge transfer to the oxygen molecule from the Pd II center. Additionally, it is observed that the presence of a protic solvent has a significant effect on the spin–orbit coupling term at the minimum energy crossing point of the triplet and singlet surfaces. Moreover, it is shown that the intermetal ligand‐transfer phenomenon is an important instance of an oxygen‐assisted S N 2 reaction.