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Computational mechanistic study of palladium(II)-catalyzed carboxyalkynylation of an olefin using an iodine(III) oxidant reagent

Citation

Ariafard, A, Computational mechanistic study of palladium(II)-catalyzed carboxyalkynylation of an olefin using an iodine(III) oxidant reagent, Organometallics, 33, (24) pp. 7318-7324. ISSN 0276-7333 (2014) [Refereed Article]

Copyright Statement

Copyright 2014 American Chemical Society

DOI: doi:10.1021/om5011758

Abstract

The Pd(II)-catalyzed chemical transformations using an iodine(III) oxidant are mostly believed to proceed via a Pd(IV)/Pd(II) catalytic cycle. The present computational study, however, demonstrates that this statement is not always true, and, in some particular cases, an alternative mechanism could be operative. Herein, the reaction mechanism of the Pd(II)-catalyzed carboxyalkynylation of an olefin using an alkynyl benziodoxolone reagent was elucidated with the aid of density functional theory calculations. The catalytic reaction was found to proceed via a mechanism in which a Pd(II) vinylidene-like complex, not a Pd(IV) complex, plays a leading role. The mechanistic understanding of the carboxyalkynylation reaction may have significant implications in a variety of processes catalyzed by transition metal complexes in the presence of alkynyl benziodoxolones.

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
Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:98776
Year Published:2014
Web of Science® Times Cited:9
Deposited By:Chemistry
Deposited On:2015-03-02
Last Modified:2017-10-25
Downloads:0

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