Water-soluble ruthenium alkylidenes: Synthesis, characterization, and application to olefin metathesis in protic solvents

Journal of the American Chemical Society

Volumn 122, Issue 28, 2000, Pages 6601-6609

  Lynn, David M ^a   Mohr, Bernhard ^a   Grubbs, Robert H ^a   Henling, Lawrence M ^a   Day, Michael W ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PHOSPHINE DERIVATIVE; RUTHENIUM DERIVATIVE; SOLVENT;

ARTICLE; METAL BINDING; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYMERIZATION; QUANTITATIVE DIAGNOSIS; REACTION ANALYSIS; SOLUBILITY; X RAY DIFFRACTION;

EID: 0034686682     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0003167     Document Type: Article

References (50)

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5. (b) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974.
6. Lynn, D. M.; Kanaoka, S.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 784.
7. For recent reports on the synthesis of new glycopolymers using alkylidene 2b in aqueous environments, see: (a) Gordon, E. J.; Sanders, W. J.; Kiessling, L. L. Nature 1998, 392, 30.
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11. For reports on the synthesis of these polymers using ill-defined ruthenium initiators, see: Mortell, K. H.; Weatherman, R. V.; Kiessling, L. L. J. Am. Chem. Soc. 1996, 118, 2297 and references therein.
12. For the application of "classical" ruthenium initiators to ROMP in aqueous media, see: (a) Hillmyer, M. A.; Lepetit, C.; McGrath, D. V.; Novak, B. M.; Grubbs, R. H. Macromolecules 1992, 25, 3345.
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16. It has been estimated that fewer than 1% of the metal centers in these ill-defined initiators are converted to catalytically active alkylidenes.
17. For recent references regarding ruthenium-catalyzed cross-metathesis, see: (a) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Grubbs, R. H. Tetrahedron Lett. 1998, 39, 7427.
18. (b) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Miura, K.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 1091.
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30. The nature of the inorganic decomposition products is not known.
31. Nguyen, S. T. Ph.D. Thesis, California Institute of Technology, 1995.
32. 1H NMR P-H coupling constant data taken from a variety of published ruthenium alkylidenes with respect to the dihedral angles between the Ru-P and alkylidene C-H bonds in these complexes (determined by X-ray diffraction analysis) does not yield a sinusiodal Karplus-type relationship. Assignment of alkylidene geometries made strictly from NMR data, therefore, should be made with discretion. Sanford, M. S.; Matzger, A. J.; Grubbs, R. H. 1999. Unpublished results.
33. Hinderling, C.; Adlhart, C.; Chen, P. Angew. Chem., Int. Ed. 1998, 37, 2685.
34. The reasons for this rapid decomposition are not entirely clear. As relatively nonpolar solvents were employed in the workup of this complex, decomposition may have resulted from the intramolecular displacement of a chloride ligand by a sulfonate group. As ruthenium alkylidenes bearing alkoxy or carboxy X-type ligands are generally less stable than halide-substituted analogues, the formation of a six-membered chelate and the precipitation of NaCl could result in rapid alkylidene decomposition.
35. 3OD. The nature of this new reaction will be reported separately in a forthcoming contribution.
36. These monomers were designed incorporating chloride counterions to alleviate potential anionic ligand exchange reactions which would alter the structure of the catalysts in these reactions.
37. Novak, B. M. Ph.D Thesis, California Institute of Technology, 1989.
38. (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis; Academic Press: London, 1997.
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43. 1H NMR integration) remained constant over the entire reaction period, providing further evidence for the absence of chain transfer reactions in these systems.
44. The propagating species in aqueous polymerizations initiated by "classical" ruthenium complexes do react with acyclic olefins under certain circumstances. For example, very high concentrations of cis-2-butene-1,4-diol or its dimethyl ether can be employed as chain transfer agents to obtain modest molecular weight control in aqueous systems (see ref 5b). In general, however, these complexes do not react with acyclic olefins and cannot be used for applications such as cross-metathesis or RCM in water or methanol.
45. Ulman, M.; Grubbs, R. H. J. Org. Chem. 1999, 64, 7202.
46. Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503.
47. For recent examples, see: (a) Reference 3. (b) Weck, M.; Schwab, P.; Grubbs, R. H. Macromolecules 1996, 29, 1789.
48. Crystallographic data (excluding structure factors) for the structure of alkylidene 6 have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC121704. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44 1223 336033. E-mail: deposit@ccdc.cam.ac.uk).
49. Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.
50. Sheldrick, G. M. SHELXL-97. Program for Structures Refinement; University of Gottingen. Federal Republic of Germany, 1997.