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Intra- and Intermolecular C−H Activation by Bis(phenolate)pyridineiridium(III) Complexes

Fu, Ross and Bercaw, John E. and Labinger, Jay A. (2011) Intra- and Intermolecular C−H Activation by Bis(phenolate)pyridineiridium(III) Complexes. Organometallics, 30 (24). pp. 6751-6765. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20120124-091855514

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Abstract

A bis(phenolate)pyridine pincer ligand (henceforth abbreviated as ONO) has been employed to support a variety of iridium complexes in oxidation states I, III, and IV. Complexes (ONO)IrL_2Me (L = PPh_3, PEt_3) react with I_2 to cleave the Ir–C bond and liberate MeI, apparently via a mechanism beginning with electron transfer to generate an intermediate Ir(IV) complex, which can be isolated and characterized for the case L = PEt_3. The PPh_3 complex is transformed in benzene at 65 °C to the corresponding phenyl complex, with loss of methane, and subsequently to a species resulting from metalation of a PPh_3 ligand. Labeling and kinetics studies indicate that PPh_3 is the initial site of C–H activation, even though the first observed product is that resulting from intermolecular benzene activation. C–H activation of acetonitrile has also been observed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om201069kDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om201069kPublisherArticle
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2011 American Chemical Society. Received: November 2, 2011. Publication Date (Web): November 29, 2011. We thank Dr. Michael W. Day and Lawrence M. Henling (Caltech) for X-ray crystallographic studies. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology, CHE-0639094. This work was supported by BP in the MC2 and XC2 programs.
Funders:
Funding AgencyGrant Number
NSFCHE-0639094
BP MC2 programUNSPECIFIED
BP XC2 ProgramUNSPECIFIED
Issue or Number:24
Record Number:CaltechAUTHORS:20120124-091855514
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20120124-091855514
Official Citation: Intra- and Intermolecular C–H Activation by Bis(phenolate)pyridineiridium(III) Complexes Ross Fu, John E. Bercaw, and Jay A. Labinger Organometallics 2011 30 (24), 6751-6765
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:28932
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:24 Jan 2012 17:37
Last Modified:03 Oct 2019 03:36

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