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Synthesis and Activity of Ruthenium Alkylidene Complexes Coordinated with Phosphine and N-Heterocyclic Carbene Ligands

Trnka, Tina M. and Morgan, John P. and Sanford, Melanie S. and Wilhelm, Thomas E. and Scholl, Matthias and Choi, Tae-Lim and Ding, Sheng and Day, Michael W. and Grubbs, Robert H. (2003) Synthesis and Activity of Ruthenium Alkylidene Complexes Coordinated with Phosphine and N-Heterocyclic Carbene Ligands. Journal of the American Chemical Society, 125 (9). pp. 2546-2558. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20170414-073637084

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Abstract

This paper reports the synthesis and characterization of a variety of ruthenium complexes coordinated with phosphine and N-heterocyclic carbene (NHC) ligands. These complexes include several alkylidene derivatives of the general formula (NHC)(PR_3)(Cl)_2Ru═CHR', which are highly active olefin metathesis catalysts. Although these catalysts can be prepared adequately by the reaction of bis(phosphine) ruthenium alkylidene precursors with free NHCs, we have developed an alternative route that employs NHC-alcohol or -chloroform adducts as “protected” forms of the NHC ligands. This route is advantageous because NHC adducts are easier to handle than their free carbene counterparts. We also demonstrate that sterically bulky bis(NHC) complexes can be made by reaction of the pyridine-coordinated precursor (NHC)(py)_2(Cl)_2Ru═CHPh with free NHCs or NHC adducts. Two crystal structures are presented, one of the mixed bis(NHC) derivative (H_2IMes)(IMes)(Cl)_2Ru═CHPh, and the other of (PCy_3)(Cl)(CO)Ru[η^2-(CH_2-C_6H_2Me_2)(N_2C_3H_4)(C_6H_2Me_3)], the product of ortho methyl C−H bond activation. Other side reactions encountered during the synthesis of new ruthenium alkylidene complexes include the formation of hydrido-carbonyl-chloride derivatives in the presence of primary alcohols and the deprotonation of ruthenium vinylcarbene ligands by KOBu^t. We also evaluate the olefin metathesis activity of NHC-coordinated complexes in representative RCM and ROMP reactions.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/ja021146wDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja021146wPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja021146wPublisherSupporting Information
ORCID:
AuthorORCID
Sanford, Melanie S.0000-0001-9342-9436
Choi, Tae-Lim0000-0001-9521-6450
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2003 American Chemical Society. Received 4 September 2002. Published online 12 February 2003. Published in print 1 March 2003. This research was supported by the U.S. National Science Foundation and the National Institutes of Health. T.M.T. acknowledges the U.S. Department of Defense for a NDSEG graduate fellowship. We thank Lawrence M. Henling (Caltech) for contributions to the crystallography and Dr. Sharad P. Hajela (Materia) for helpful discussions.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
NIHUNSPECIFIED
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Record Number:CaltechAUTHORS:20170414-073637084
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170414-073637084
Official Citation:Synthesis and Activity of Ruthenium Alkylidene Complexes Coordinated with Phosphine and N-Heterocyclic Carbene Ligands Tina M. Trnka, John P. Morgan, Melanie S. Sanford, Thomas E. Wilhelm, Matthias Scholl, Tae-Lim Choi, Sheng Ding, Michael W. Day, and Robert H. Grubbs Journal of the American Chemical Society 2003 125 (9), 2546-2558 DOI: 10.1021/ja021146w
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76565
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:14 Apr 2017 16:09
Last Modified:14 Apr 2017 16:09

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