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Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media

Nguyen, SonBinh T. and Johnson, Lynda K. and Grubbs, Robert H. and Ziller, Joseph W. (1992) Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media. Journal of the American Chemical Society, 114 (10). pp. 3974-3975. ISSN 0002-7863. doi:10.1021/ja00036a053. https://resolver.caltech.edu/CaltechAUTHORS:20180724-152025651

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Abstract

During the past two decades, intense research efforts have enabled an in-depth understanding of the olefin metathesis reaction as catalyzed by early transition metal complexes. In contrast, the nature of the intermediates and the reaction mechanism for group VIII transition metal metathesis catalysts remain elusive. Such knowledge is important in view of the promise group VIII metals show in polymerizing a wide variety of functionalized cyclic olefins in protic solvents. Highly active late transition metal catalysts should also open the way to the metathesis of functionalized acyclic olefins. Previous studies in our group have focused on the chemistry of highly active, functional-group-tolerant catalysts prepared from aquoruthenium(II) olefin complexes. In these systems, characterization of the catalytic intermediates is difficult due to their very low concentrations and high activity in the reaction mixtures. Although it is reasonable to assume that the active species are ruthenacyclobutanes and ruthenium carbenes (ruthenaolefins), the oxidation state and ligation of these intermediates are not known. Furthermore, the discrete ruthenium carbene complexes that have been isolated to date do not exhibit both metathesis activity and stability to protic/aqueous solvents. We report here the reaction of an Ru(II) complex with a strained olefin to produce a carbene species that polymerizes norbornene in organic media both in the absence and presence of protic/aqueous solvents. In both solvent systems, a stable propagating carbene complex can be observed throughout the course of the polymerization, as has been previously found with titanium, tantalum, tungsten, molybdenum, and ruthenium complexes.


Item Type:Article
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URLURL TypeDescription
https://doi.org/10.1021/ja00036a053DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ja00036a053PublisherSupporting Information
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 1992 American Chemical Society. Received January 13, 1992. Financial support from the National Science Foundation and Du Pont is gratefully acknowledged. L.K.J. thanks the NSF for an NSF Predoctoral Fellowship. S.T.N. thanks the Department of Defense, Office of Army Research, for an NDSEG Predoctoral Fellowship and Caltech for an Institute Fellowship. Funds for the purchase of the Siemens R3m/V diffractometer system were made available from the National Science Foundation under Grant CHE-85-14495. We thank Dominic V. McGrath for helpful discussions.
Funders:
Funding AgencyGrant Number
NSF Predoctoral FellowshipUNSPECIFIED
E. I. DuPont de Nemours and Company, Inc.UNSPECIFIED
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
CaltechUNSPECIFIED
NSFCHE-85-14495
Issue or Number:10
DOI:10.1021/ja00036a053
Record Number:CaltechAUTHORS:20180724-152025651
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180724-152025651
Official Citation:Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media SonBinh T. Nguyen, Lynda K. Johnson, Robert H. Grubbs, and Joseph W. Ziller Journal of the American Chemical Society 1992 114 (10), 3974-3975 DOI: 10.1021/ja00036a053
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88217
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 Jul 2018 16:57
Last Modified:16 Nov 2021 00:25

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