Catalytic Organometallic Chemistry in Water: The Aqueous Ring-Opening Metathesis Polymerization of 7-Oxanorbornene Derivatives

Journal of the American Chemical Society

Volumn 110, Issue 22, 1988, Pages 7542-7543

  Novak, Bruce M ^a   Grubbs, Robert H ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS--ORGANOMETALLICS; OSMIUM COMPOUNDS; POLYMERIZATION--CATALYSTS; POLYMERS--SYNTHESIS; RUTHENIUM COMPOUNDS--SOLUTIONS;

CATALYST RECYCLABILITY; METAL CARBENES; OXANORBORNENE DERIVATIVES; RING-OPENING METATHESIS POLYMERIZATION; TOLUENESULFONATE;

MONOMERS;

EID: 0024088699     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00230a047     Document Type: Article

References (14)

1. Parshall, G. W. Homogeneous Catalysis; Wiley: New York, 1980.
2. (a) Ziegler, K. Angew. Chem. 1955, 65, 426. (b) Kuntz, E. G. CHEMTECH 1987, 570. (c) Chung, T. C. Macromolecules 1988, 21, 865.
3. For recent references on metathesis, see: (a) Ivin, K. J. Olefin Metathesis; Academic Press: London, 1983. (b) Grubbs, R. H. In Comprehensive Organometallic Chemistry; Wilkinson, G., Ed.; Pergamon Press, Ltd.: Oxford, 1982; Vol. 8, pp 499–551.
4. For examples of catalysis by group VIII complexes in organic solvents, see: (a) Ho, H. T.; Ivin, K. J.; Rooney, J. J. J. Mol. Catal. 1982, 15, 245. (b) Porri, L.; Diversi, P.; Lucherini, A.; Rossi, R. Makromol. Chem. 1975, 176, 3131. (c) Porri, L.; Rossi, R.; Diversi, P.; Lucherini, A. Makromol. Chem. 1974, 175, 3097.
5. Early attempts at emulsion ROMP systems have been reported. These systems, however, either fail for many monomers or, at best, give low yields of polymer (typically less than 9%). See: Rhinehart, R. E.; Smith, H. P. Polym. Lett. 1965, 3, 1049.
6. (a) Novak, B. M.; Grubbs, R. H. Proc. Am. Chem. Soc. Div. PMSE 1987, 57, 651. (b) Novak, B. M.; Grubbs, R. H. J. Am. Chem. Soc. 1988, 110, 960.
7. 3+ is used. See: Seddon, E. A.; Seddon, K. R. The Chemistry of Ruthenium', Elsevier: New York, 1984; pp 159.
8. (a) Ivin, K. J. Olefin Metathesis; Academic Press: London, 1983; pp 43–78. (b) Grubbs, R. H. In Comprehensive Organometallic Chemistry; Wilkinson, G., Ed.; Pergamon Press, Ltd.: Oxford, 1982; Vol. 8, pp 499–551.
9. w= 3.38 x 105to 1.34 x 106and the polydispersity (PDI) drops from 1.97 to 1.2 upon changing from organic to aqueous solvents. See: (a) Odian, G. Principles of Polymerization, 2d ed.; Wiley-Interscience: New York, 1981; p 319. (b) Hiemenz, P. C. Polymer Chemistry; Marcel Dekker, Inc.: New York, 1984; p 396.
10. (a) Bernhard, P.; Lehmann, H.; Ludi, A. J. Chem. Soc., Chem. Commun. 1981, 1216. (b) Bernhard, P.; Burgi, H. B.; Hauser, J.; Lehmann, H.; Ludi, A. Inorg. Chem. 1982, 21, 3936.
11. 2+ state by 1.08 V. For a discussion of the stabilization of low valent Ru complexes by electron acceptor ligands, see: Sullivan, B. P.; Baumann, J. A.; Meyer, T. J.; Salmon, D. J.; Lehmann, H.; Ludi, A. J. Am. Chem. Soc. 1977, 99, 7368.
12. Seddon, E. A.; Seddon, K. R. The Chemistry of Ruthenium; Elsevier: New York, 1984.
13. 3 reacts rapidly to form the mixed valent trimer “Ru Red”. See: (a) Fletcher, J. M.; Greenfield, B. F.; Hardy, C. J.; Scargill, D.; Woodhead, J. L. J. Chem. Soc. 1961, 2000. (b) Sterling, C. Amer. J. Bot. 1970, 57, 172. (c) Smith, P. M.; Fealey, T.; Earley, J. E.; Silverton, J. V. Inorg. Chem. 1971, 10, 1943.
14. Several Ru2+ olefin complexes are known. See: (a) Sullivan, B. P.; Baumann, J. A.; Meyer, T. J.; Salmon, D. J.; Lehmann, H.; Ludi, A. J. Am. Chem. Soc. 1977, 99, 7368. (b) Lehmann, H.; Schenk, K. J.; Chapuis, G.; Ludi, A. J. Am. Chem. Soc. 1979, 101, 6197.