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Novel Reactivity of Ruthenium Alkylidenes in Protic Solvents: Degenerate Alkylidene Proton Exchange

Lynn, David M. and Grubbs, Robert H. (2001) Novel Reactivity of Ruthenium Alkylidenes in Protic Solvents: Degenerate Alkylidene Proton Exchange. Journal of the American Chemical Society, 123 (14). pp. 3187-3193. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170414-073636763

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Abstract

A novel organometallic transformation is reported in which the alkylidene protons of water-soluble ruthenium alkylidenes 1 and 2 undergo nondestructive, degenerate exchange with solvent-derived deuterons in perdeuterated protic solvents such as D_2O and CD_3OD. Deuterated alkylidene complex (1-D) was isolated from a solution of alkylidene 1 in D_2O, and the new alkylidene was fully characterized by ^1H, ^2H, ^(13)C, and ^(31)P NMR spectroscopy and fast-atom bombardment mass spectroscopy (FAB-MS). The rate of alkylidene proton exchange for this transformation was found to correlate with the bulk dielectric constant of the solvent or solvent mixtures employed. The data support a mechanism for proton exchange involving the dissociation of a chloride ion from the ruthenium metal center. The rate of alkylidene H/D exchange for alkylidene 2 was faster than the rate of exchange for alkylidene 1, demonstrating that relative rates of exchange are influenced by the electron densities at the metal centers of these complexes. Several additional ruthenium alkylidenes were found to undergo analogous alkylidene H/D exchange reactions, including parent alkylidene (Cy_3P)_2Cl_2Ru═CHPh (3) in CD_2Cl_2/CD_3OD mixtures. These data suggest that this novel reactivity may be general for an entire class of ruthenium alkylidenes provided that protic species are available in solution and that the dielectric constant of the reaction medium is sufficiently high to ionize the halide ligands.


Item Type:Article
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http://dx.doi.org/10.1021/ja0020299DOIArticle
http://pubs.acs.org/doi/full/10.1021/ja0020299PublisherArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2001 American Chemical Society. Received 7 June 2000. Published online 15 March 2001. Published in print 1 April 2001. The authors wish to thank Drs. Eric Dias, Bernhard Mohr, Adam Matzger, Thomas Rölle, and Melanie Sanford for helpful discussions and insight. Dr. Robert Lee is thanked for his assistance with deuterium-decoupled ^(13)C NMR spectroscopy experiments. This work was supported by the NSF.
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Issue or Number:14
Record Number:CaltechAUTHORS:20170414-073636763
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170414-073636763
Official Citation:Novel Reactivity of Ruthenium Alkylidenes in Protic Solvents:  Degenerate Alkylidene Proton Exchange David M. Lynn and Robert H. Grubbs Journal of the American Chemical Society 2001 123 (14), 3187-3193 DOI: 10.1021/ja0020299
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76564
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:14 Apr 2017 16:02
Last Modified:03 Oct 2019 17:02

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