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Electrophilic Rh^I catalysts for arene H/D exchange in acidic media: evidence for an electrophilic aromatic substitution mechanism

Webster-Gardiner, Michael S. and Piszel, Paige E. and Fu, Ross and McKeown, Bradley A. and Nielsen, Robert J. and Goddard, William A., III and Gunnoe, T. Brent (2017) Electrophilic Rh^I catalysts for arene H/D exchange in acidic media: evidence for an electrophilic aromatic substitution mechanism. Journal of Molecular Catalysis A: Chemical , 426 . pp. 381-388. ISSN 1381-1169. https://resolver.caltech.edu/CaltechAUTHORS:20160803-142334974

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Abstract

A series of new rhodium (I) complexes supported by bidentate nitrogen-donor ligands with varying electronic and steric properties were synthesized in situ and evaluated for catalytic arene C−H/D activation. In trifluoroacetic acid (HTFA), these complexes are proposed to mediate H/D exchange of arene C−H/D bonds by an electrophilic aromatic substitution mechanism that involves Rh-mediated activation of HTFA (or DTFA). DFT calculations support the proposed pathway for the H/D exchange reactions.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/j.molcata.2016.07.045DOIArticle
http://www.sciencedirect.com/science/article/pii/S1381116916302953PublisherArticle
ORCID:
AuthorORCID
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2016 Elsevier. Received 27 June 2016, Revised 23 July 2016, Accepted 25 July 2016, Available online 1 August 2016. The authors acknowledge the National Science Foundation (CHE-1465145, TBG; NSF CHE-1214158, WAG) for financial support. M.S.W-G. acknowledges support from AES for a graduate student fellowship, the Jefferson Scholars Foundation for a dissertation year fellowship and Junqi Chen for assistance with an experimental procedure.
Funders:
Funding AgencyGrant Number
NSFCHE-1465145
NSFCHE-1214158
AES Graduate Student FellowshipUNSPECIFIED
Jefferson Scholars FoundationUNSPECIFIED
Subject Keywords:Rhodium, C–H Activation, Arene, Acid, Electrophilic
Record Number:CaltechAUTHORS:20160803-142334974
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160803-142334974
Official Citation:Michael S. Webster-Gardiner, Paige E. Piszel, Ross Fu, Bradley A. McKeown, Robert J. Nielsen, William A. Goddard III, T. Brent Gunnoe, Electrophilic RhI catalysts for arene H/D exchange in acidic media: Evidence for an electrophilic aromatic substitution mechanism, Journal of Molecular Catalysis A: Chemical, Volume 426, Part B, January 2017, Pages 381-388, ISSN 1381-1169, http://dx.doi.org/10.1016/j.molcata.2016.07.045. (//www.sciencedirect.com/science/article/pii/S1381116916302953)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:69418
Collection:CaltechAUTHORS
Deposited By: Donna Wrublewski
Deposited On:03 Aug 2016 23:44
Last Modified:03 Oct 2019 10:21

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