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Computational study of intramolecular coordination enhanced oxidative addition to form PdIV-pincer complexes, and selectivity in aryloxide attack at PdIVCH2CRR′ motifs in palladium-mediated organic synthesis

Citation

Canty, AJ and Ariafard, A, Computational study of intramolecular coordination enhanced oxidative addition to form PdIV-pincer complexes, and selectivity in aryloxide attack at PdIVCH2CRR′ motifs in palladium-mediated organic synthesis, Organometallics, 40, (9) pp. 1262-1269. ISSN 0276-7333 (2021) [Refereed Article]

Copyright Statement

Copyright 2021 American Chemical Society

DOI: doi:10.1021/acs.organomet.1c00058

Abstract

Computational studies support the key role of intramolecular coordination by a carboxylate group in the facile oxidative addition of the iodoarene 2,6-(HO2C)2C6H3I to a PdII center to form the pincer-PdIV motif Pd{2,6(O2C)C6H3-O,C,O}, Pd(OCO). Mechanisms of attack by an aryloxide nucleophile at the methylene group in a palladacycle PdIV(OCO)(CH2CRR′E) to form ArOCH2CMe2E (E = oxime) are examined; for RR′ = HEt and E = amine, it is mainly the formation of analogous ArOCH2CHEtE together with CH2═CEtE arising from β-hydrogen elimination. Computational results are in agreement with recent experimental results by Whitehurst, Gaunt. [J. Am. Chem. Soc. 2020, 142, 14169]. For β-hydrogen elimination, computation demonstrates that the conformational flexibility in the chelate ring is required to allow the hydrogen atom to be in an axial orientation relative to PdC, thus maximizing the dihedral angle PdCCH in the transition-state fragment PdCH2C(R)HOAr. Bulky substituents R′ at the β-position, CHR′, favor nucleophilic attack at the methylene carbon.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:144365
Year Published:2021
Web of Science® Times Cited:1
Deposited By:Chemistry
Deposited On:2021-05-18
Last Modified:2021-07-28
Downloads:0

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