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Heterolytic carbon–iodine bond cleavage by palladium(i) metalloradical
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Sinclair, Matthew J. G. and Chaplin, Adrian B. (2022) Heterolytic carbon–iodine bond cleavage by palladium(i) metalloradical. Dalton Transactions, 51 (31). pp. 11617-11619. doi:10.1039/d2dt02152h ISSN 1477-9234.
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Official URL: https://doi.org/10.1039/d2dt02152h
Abstract
The well-defined Pd(I) metalloradical [Pd(PtBu3)2]+ reacts with aryl and alkyl iodides at room temperature, yielding [Pd(PtBu3)(μ-I)]2 and phosphonium salts. Pd(II) aryl/alkyl derivates, reflecting net radical oxidative addition of the substrate to the metalloradical, are generated during the reaction and two examples have been isolated and crystallographically characterised.
The transition-metal-mediated activation of carbon–halogen bonds is the basis of widely exploited catalytic methods for the construction of organic molecules. Oxidative addition to low-coordinate Pd(0) complexes is a pervading theme, with work by Hartwig and co-workers in 2002 involving isolation of T-shaped aryl Pd(ii) halide products a key mechanistic reference point (Scheme 1A).1,2 Whilst the Pd(0)/Pd(ii) redox couple remains the workhorse, processes invoking single electron transfer and Pd(i) and Pd(iii) intermediates have been attracting growing attention.3 Well-defined monomeric examples of the former are rare,4 but as part of work in our group we recently reported the synthesis of [Pd(PtBu3)2][PF6] 1 by one-electron oxidation of [Pd(PtBu3)2] with [Fc][PF6].5 Using 1 as an exemplar, we herein present our preliminary findings exploring the activation of aryl and alkyl iodides by palladium metalloradicals.
Item Type: | Journal Article | ||||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||
SWORD Depositor: | Library Publications Router | ||||||
Journal or Publication Title: | Dalton Transactions | ||||||
Publisher: | Royal Society of Chemistry (RSC) | ||||||
ISSN: | 1477-9234 | ||||||
Official Date: | 11 July 2022 | ||||||
Dates: |
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Volume: | 51 | ||||||
Number: | 31 | ||||||
Page Range: | pp. 11617-11619 | ||||||
DOI: | 10.1039/d2dt02152h | ||||||
Status: | Peer Reviewed | ||||||
Publication Status: | Published | ||||||
Reuse Statement (publisher, data, author rights): | ** Article version: VoR ** From Crossref journal articles via Jisc Publications Router ** Licence for VoR version of this article starting on 11-07-2022: http://creativecommons.org/licenses/by/3.0/ | ||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||
Date of first compliant deposit: | 17 August 2022 | ||||||
Date of first compliant Open Access: | 17 August 2022 | ||||||
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