Controlled Living Ring-Opening-Metathesis Polymerization by a Fast-Initiating Ruthenium Catalyst†
Tae-Lim Choi
Arnold and Mabel Laboratories of Chemical Synthesis, California Institute of Technology, Division of Chemistry and Chemical Engineering, MC 164-30 Pasadena, CA 91125, USA, Fax: (+1) 626-564-9297
Search for more papers by this authorRobert H. Grubbs Prof.
Arnold and Mabel Laboratories of Chemical Synthesis, California Institute of Technology, Division of Chemistry and Chemical Engineering, MC 164-30 Pasadena, CA 91125, USA, Fax: (+1) 626-564-9297
Search for more papers by this authorTae-Lim Choi
Arnold and Mabel Laboratories of Chemical Synthesis, California Institute of Technology, Division of Chemistry and Chemical Engineering, MC 164-30 Pasadena, CA 91125, USA, Fax: (+1) 626-564-9297
Search for more papers by this authorRobert H. Grubbs Prof.
Arnold and Mabel Laboratories of Chemical Synthesis, California Institute of Technology, Division of Chemistry and Chemical Engineering, MC 164-30 Pasadena, CA 91125, USA, Fax: (+1) 626-564-9297
Search for more papers by this authorThe authors would like to thank the National Science Foundation for generous support of this research, and D. Benitez, D. P. Sanders, J. P. Morgan, and O. A. Scherman for helpful discussions, and A. Hejl for the generous supply of catalyst 4.
Graphical Abstract
Hoch aktiver Katalysator, ultraschnelle Initiation: Der Katalysator 1 vermittelt die lebende Ringöffnungspolymerisation von Norbornen- und 7-Oxonorbornen-Derivaten (siehe Schema). Das hohe Verhältnis ki/kp, das dabei mit 1 erreicht wird, führt zu besonders guter Steuerung des Molekulargewichts und zu einem niedrigen Polydispersitätsindex (PDI).
References
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- 14This PNB contained 61 % of the cis-olefin isomer and is much higher than PNB produced with 3 (35 % cis), which undergoes chain-transfer reactions.[8 b]
- 15Ten equivalents of 8 were mixed with 4 at −10 °C resulting in complete initiation (the only propagating carbene signal in the corresponding 13C NMR spectrum was observed at δ=18.2 ppm) and 13 % product conversion. Based on the assumption of at least 99 % initiation, a minimum value of ki/kp=19 is calculated by using the Gold equation. See reference [1 b] page 232.
- 16Complexes with other substituted-pyridine ligands can show similar rapid initiation rates A. Hejl, R. Grubbs, unpublished results.
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