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Mechanism of C−F Reductive Elimination from Palladium(IV) Fluorides

Furuya, Takeru and Benitez, Diego and Tkatchouk, Ekaterina and Strom, Alexandra E. and Tang, Pingping and Goddard, William A., III and Ritter, Tobias (2010) Mechanism of C−F Reductive Elimination from Palladium(IV) Fluorides. Journal of the American Chemical Society, 132 (11). pp. 3793-3807. ISSN 0002-7863. PMCID PMC2852535. https://resolver.caltech.edu/CaltechAUTHORS:20100415-110315725

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Abstract

The first systematic mechanism study of C−F reductive elimination from a transition metal complex is described. C−F bond formation from three different Pd(IV) fluoride complexes was mechanistically evaluated. The experimental data suggest that reductive elimination occurs from cationic Pd(IV) fluoride complexes via a dissociative mechanism. The ancillary pyridyl-sulfonamide ligand plays a crucial role for C−F reductive elimination, likely due to a κ^3 coordination mode, in which an oxygen atom of the sulfonyl group coordinates to Pd. The pyridyl-sulfonamide can support Pd(IV) and has the appropriate geometry and electronic structure to induce reductive elimination.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ja909371tDOIArticle
https://doi.org/10.1021/ja102348wDOIAddition/Correction
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2852535PubMed CentralArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2010 American Chemical Society. Published In Issue: March 24, 2010; article ASAP: March 02, 2010; received: November 4, 2009. We acknowledge NIH-NIGMS (GM088237) for financial support of this project. We thank Dr. Shaw Huang for NMR analysis, Dr. Douglas M. Ho and Jessica Y. Wu for X-ray crystallographic analysis, Dr. Imhyuck Bae and Christian A. Kuttruff for discussions, Chenghong Huang for experimental contributions, and Air Products and Chemicals, Inc. for a generous donation of F-TEDA-BF4. Computational facilities were funded by grants from ARO-DURIP and ONR-DURIP.
Funders:
Funding AgencyGrant Number
NIHGM088237
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:11
PubMed Central ID:PMC2852535
Record Number:CaltechAUTHORS:20100415-110315725
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20100415-110315725
Official Citation:Mechanism of C−F Reductive Elimination from Palladium(IV) Fluorides Takeru Furuya, Diego Benitez, Ekaterina Tkatchouk, Alexandra E. Strom, Pingping Tang, William A. Goddard III, Tobias Ritter Journal of the American Chemical Society 2010 132 (11), 3793-3807
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:17994
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:16 Apr 2010 14:54
Last Modified:03 Oct 2019 01:36

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