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Intramolecular C–H and C–F Bond Oxygenation Mediated by a Putative Terminal Oxo Species in Tetranuclear Iron Complexes

De Ruiter, Graham and Thompson, Niklas B. and Takase, Michael K. and Agapie, Theodor (2016) Intramolecular C–H and C–F Bond Oxygenation Mediated by a Putative Terminal Oxo Species in Tetranuclear Iron Complexes. Journal of the American Chemical Society, 138 (5). pp. 1486-1489. ISSN 0002-7863. PMCID PMC4871154. http://resolver.caltech.edu/CaltechAUTHORS:20160208-092710615

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Abstract

Herein we report the intramolecular arene C–H and C–F bond oxygenation by tetranuclear iron complexes. Treatment of [LFe_3(PhPz)_3OFe][OTf]_2 (1) or its fluorinated analog [LFe_3(F2ArPz)_3OFe][OTf]_2 (5) with iodosobenzene results in the regioselective hydroxylation of a bridging pyrazolate ligand, converting a C–H or C–F bond into a C–O bond. The observed reactivity suggests the formation of terminal and reactive Fe-oxo intermediates. With the possibility of intramolecular electron transfer within clusters in 1 and 5, different reaction pathways (Fe^(IV)-oxo vs Fe^(III)-oxo) might be responsible for the observed arene hydroxylation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.5b12214DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.5b12214PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.5b12214PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4871154/PubMed CentralArticle
ORCID:
AuthorORCID
Thompson, Niklas B.0000-0003-2745-4945
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2016 American Chemical Society. Received: November 22, 2015. Article ASAP. Publication Date (Web): January 13, 2016. This research was supported by the NIH (R01-GM102687A). T.A. is grateful for Sloan, Dreyfus, and Cottrell fellowships. T.A. and G. de R. are grateful for a Camille & Henry Dreyfus Environmental Chemistry Fellowship. We thank Lawrence M. Henling for assistance with crystallography. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01-GM102687A
Alfred P. Sloan FoundationUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Cottrell Scholar of Research CorporationUNSPECIFIED
PubMed Central ID:PMC4871154
Record Number:CaltechAUTHORS:20160208-092710615
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160208-092710615
Official Citation:ntramolecular C–H and C–F Bond Oxygenation Mediated by a Putative Terminal Oxo Species in Tetranuclear Iron Complexes Graham de Ruiter, Niklas B. Thompson, Michael K. Takase, and Theodor Agapie Journal of the American Chemical Society 2016 138 (5), 1486-1489 DOI: 10.1021/jacs.5b12214
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64298
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:08 Feb 2016 17:46
Last Modified:27 Nov 2017 21:37

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