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Reaction of Tp(PPh_3)Ru(η^2-O_2CCHPh_2) with Carbene and Vinylidene Precursors

Sanford, Melanie S. and Valdez, Michelle R. and Grubbs, Robert H. (2001) Reaction of Tp(PPh_3)Ru(η^2-O_2CCHPh_2) with Carbene and Vinylidene Precursors. Organometallics, 20 (25). pp. 5455-5463. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20170808-084706910

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Abstract

Tp(PPh_3)Ru(η^2-O_2CCHPh_2) (1) [Tp = tris(pyrazolyl)borate] has been prepared by the reaction of TpRu(Cl)(PPh_3)_2 with 1.2 equiv of NaO_2CCHPh_2. Complex 1 reacts with diphenylcyclopropene to generate the metallacycle Tp(PPh_3)Ru[κ^2-(C,Ο)-C(═CHCHPh_2)OC(CHPh_2)═O] (2). A trace of the carbene Tp(PPh_3)(η^1-O_2CCHPh_2)Ru═CHCH═C(Ph)_2 (3) is also observed in the crude reaction mixture. Compound 1 reacts with phenyldiazomethane to form the benzylidene Tp(PPh_3)(η^1-O_2CCHPh_2)Ru═CHPh (4). A similar species is also available by the reaction between AgO_2CCHPh_2 and Tp(PCy_3)(Cl)Ru═CHCH═C(CH_3)_2 (5), which affords Tp(PCy_3)(η^1-O_2CCHPh_2)Ru═CHCH═C(CH_3)_2 (6). With the addition of an excess of HCl, complexes 4 and 6 release free HO_2CCHPh_2 and are converted to Tp(PPh_3)(Cl)Ru═CHPh (7) and complex 5, respectively. The reaction of 1 with phenylacetylene yields the five-membered chelate Tp(PPh_3)Ru[κ^2-(C,Ο)-C(═CHPh)OC(CHPh_2)═O] (8). Complex 8 is also formed in the reaction of Tp(PPh_3)(Cl)Ru═C═CHPh with 1.2 equiv of AgO_2CCHPh_2. Compounds 1, 2, and 8 have been characterized by X-ray crystallography. Complexes 2, 5, 6, 7, and 8 do not catalyze olefin metathesis reactions, while 4 is an active initiator for the ring-opening metathesis polymerization of norbornene.


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URLURL TypeDescription
http://dx.doi.org/10.1021/om010558vDOIArticle
http://pubs.acs.org/doi/full/10.1021/om010558vPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om010558vPublisherSupporting Information
ORCID:
AuthorORCID
Sanford, Melanie S.0000-0001-9342-9436
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2001 American Chemical Society. Received 25 June 2001. Published online 6 November 2001. Published in print 1 December 2001. Lawrence M. Henling and Michael W. Day are gratefully acknowledged for carrying out the X-ray crystallographic studies described herein. The authors also would like to thank Bill Ward and Arnab Chatterjee for critical reading of the manuscript. M.R.V. acknowledges the Caltech SURF program for a summer fellowship. This work was supported by the National Science Foundation.
Funders:
Funding AgencyGrant Number
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
NSFUNSPECIFIED
Issue or Number:25
Record Number:CaltechAUTHORS:20170808-084706910
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170808-084706910
Official Citation:Reaction of Tp(PPh3)Ru(η2-O2CCHPh2) with Carbene and Vinylidene Precursors Melanie S. Sanford, Michelle R. Valdez, and Robert H. Grubbs Organometallics 2001 20 (25), 5455-5463 DOI: 10.1021/om010558v
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79910
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:09 Aug 2017 20:36
Last Modified:03 Oct 2019 18:25

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