Publication: Providing Support in Favor of the Existence of a PdII/PdIV Catalytic Cycle in a Heck-Type Reaction
Authors
Juliá Hernández, Francisco ; Arcas, Aurelia ; Vicente, José
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Publisher
Wiley
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DOI
10.1002/chem.201103679
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info:eu-repo/semantics/article
Description
©2012. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
This document is the Accepted, version of a Published Work that appeared in final form in Chem. Eur. J. To access the final edited and published work see https://doi.org/10.1002/chem.201103679
Abstract
The complex [Pd(O,N,C-L)(OAc)], where L is a monoanionic pincer ligand derived from 2,6-diacetylpyridine, reacts with IBzOH at room temperature to afford the very stable pair of PdIV complexes (OC-6-54)- and (OC-6-26)-[Pd(O,N,C-L)(O,CC6H4CO2-2)I] (1.5:1 molar ratio, at –55 ºC). These complexes and the PdII species [Pd(O,N,C-L)(OX)] and [Pd(O,N,C-L’)(NCMe)]ClO4, (X = MeC(O) or ClO3, L’ = another monoanionic pincer ligand derived from 2,6-diacetylpyridine), are precatalysts for the arylation of CH2=CHR (R = CO2Me, CO2Et, Ph) using IC6H4CO2H-2 and AgClO4. These catalytic reactions have been studied and a tentative mechanism is proposed. The presence of two PdIV complexes is detected by ESI(+)-MS during the catalytic process. All data obtained strongly support a PdII/PdIV catalytic cycle.
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Citation
Chem. Eur. J. 2012, 18 (25), 7780-7786
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