Mechanism of C−F Reductive Elimination from Palladium(IV) Fluorides
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.
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.Attached Files
Accepted Version - nihms184744.pdf
Supplemental Material - ja909371t_si_001.pdf
Supplemental Material - ja909371t_si_002.cif
Supplemental Material - ja909371t_si_003.cif
Files
Additional details
- PMCID
- PMC2852535
- Eprint ID
- 17994
- Resolver ID
- CaltechAUTHORS:20100415-110315725
- GM088237
- NIH
- Army Research Office (ARO)
- Office of Naval Research (ONR)
- Created
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2010-04-16Created from EPrint's datestamp field
- Updated
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2023-06-01Created from EPrint's last_modified field