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Carboxylate-Assisted C(sp^3)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes

Cannon, Jeffrey S. and Zou, Lufeng and Liu, Peng and Lan, Yu and O'Leary, Daniel J. and Houk, K. N. and Grubbs, Robert H. (2014) Carboxylate-Assisted C(sp^3)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes. Journal of the American Chemical Society, 136 (18). pp. 6733-6743. ISSN 0002-7863. PMCID PMC4017616. http://resolver.caltech.edu/CaltechAUTHORS:20140506-091313925

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Abstract

The mechanism of C–H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C–H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation–deprotonation mechanism with ΔG^(‡)_(298K) = 22.2 ± 0.1 kcal·mol^(–1) for the parent N-adamantyl-N′-mesityl complex. An experimentally determined ΔS^(‡) = −5.2 ± 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp^3)–H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k_(H)/k_(D) = 8.1 ± 1.7), agree closely with a computed six-membered carboxylate-assisted C–H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja5021958DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja5021958PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja5021958PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4017616/PubMed CentralArticle
ORCID:
AuthorORCID
Liu, Peng0000-0002-8188-632X
Houk, K. N.0000-0002-8387-5261
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice. Received: March 3, 2014; Published: April 14, 2014. This work was financially supported by the NIH (NIH R01-GM031332 and NRSA to J.S.C.: F32-GM103002), the NSF (CHE-1212767, CHE-1059084), and the NSF CCI Center for Stereoselective C−H Functionalization (CHE-1205646). NMR spectra were obtained by instruments supported by the NIH (RR027690). Materia, Inc. is acknowledged for the generous donation of complex 4b. D.J.O. thanks Pomona College for supporting a portion of this research. Calculations were performed on the Hoffman2 cluster at UCLA and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF. K. M. Engle, J. Hartung, and Z. K. Wickens are gratefully acknowledged for helpful discussions.
Funders:
Funding AgencyGrant Number
NIHR01-GM031332
NIH Predoctoral FellowshipF32-GM103002
NSFCHE-1205646
NIHRR027690
Pomona CollegeUNSPECIFIED
NSFCHE-1212767
NSFCHE-1059084
PubMed Central ID:PMC4017616
Record Number:CaltechAUTHORS:20140506-091313925
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140506-091313925
Official Citation:Carboxylate-Assisted C(sp3)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes Jeffrey S. Cannon, Lufeng Zou, Peng Liu, Yu Lan, Daniel J. O’Leary, K. N. Houk, and Robert H. Grubbs Journal of the American Chemical Society 2014 136 (18), 6733-6743
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45515
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:06 May 2014 18:17
Last Modified:10 Oct 2017 17:32

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