Measurement of the rate constant for H. abstraction from methylisobutyryl radical by (C5Ph5)Cr(CO)3 .

Macromolecules

Volumn 39, Issue 24, 2006, Pages 8236-8240

  Tang, Lihao ^a   Norton, Jack R ^a  

^a Howard Hughes Medical Institute   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

METALLORADIC; THERMOLYSIS; TRANSFER RATE CONSTANT;

CONCENTRATION (PROCESS); CRYSTAL GROWTH; HEATING; INORGANIC COMPOUNDS; PHASE TRANSITIONS; POLYMERIZATION;

REACTION KINETICS;

EID: 33846124224     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma0615755     Document Type: Article

References (38)

1. Gridnev, A. A.; Ittel, S. D. Chem. Rev. 2001, 101, 3611-3659.
2. Mayo, F. R. J. Am. Chem. Soc. 1943, 65, 2324-2329.
3. Gridnev, A. A.; Bel'govskii, I. M.; Enykolopyan, N. S. Vysokomol. Soedin., Ser. B (Polym. Sci.) 1986, B28, 85 (Russian);
4. Chem. Abstr. 1986, 105, 6846.
5. Smith, G. B.; Heuts, J. P. A.; Russell, G. T. Macromol. Symp. 2005, 226, 133-146.
6. 3H and a vinyl-terminated macromonomer decreases as the chain length increases. See: Tang, L. Scope and Mechanism of Chain Transfer Catalysis with Metalloradicals and Metal Hydrides. Ph.D. Thesis, Columbia University, New York, 2005.
7. Smirnov, B. R.; Marchenko, A. P.; Plotnikov, V. D.; Kuzayev, A. I.; Yenikolopyan, N. S. Polym. Sci. U.S.S.R. 1981, 23, 1169-1178.
8. Burczyk, A. F.; O'Driscoll, K. F.; Rempel, G. L. J. Polym. Sci., Polym. Chem. Ed. 1984, 22, 3255-3262.
9. Sanayei, R. A.; O'Driscoll, K. F. J. Macromol, Sci., Chem. 1989, A26, 1137-1149.
10. Olaj, O. F.; Zoder, M.; Vana, P.; Kornherr, A.; Schnöll-Bitai, I.; Zifferer, G. Macromolecules 2005, 38, 1944-1948 and references therein.
11. Gridnev, A. A.; Ittel, S. D. Macromolecules 1996, 29, 5864-5874.
12. Beuermann, S.; Buback, M.; Davis, T. P.; Gilbert, R. G.; Hutchinson, R. A.; Olaj, O. F.; Russell, G. T.; Schweer, J.; van Herk, A. M. Macromol. Chem. Phys. 1997, 198, 1545-1560.
13. Tang, L.; Papish, E. T.; Abramo, G. P.; Norton, J. R.; Baik, M.-H.; Friesner, R. A.; Rappé, A. J. Am. Chem. Soc. 2003, 125, 10093-10102;
14. 2006, 128, 11314.
15. Tang, L.; Norton, J. R.; Edwards, J. C. Macromolecules 2003, 36, 9716-9720.
16. Tang, L.; Norton, J. R. Macromolecules 2004, 37, 241-243.
17. Tang, L.; Norton, J. R., submitted to Macromolecules.
18. Smith, G. B.; Russell, G. T.; Heuts, J. P. A. Macromol. Theory Simul. 2003, 12, 299-314.
19. Stickler, M. Makromol. Chem. 1986, 187, 1765-1775.
20. Korth, H. G.; Lommes, P.; Sicking, W.; Sustmann, R. Int. J. Chem. Kinet. 1983, 15, 267-279.
21. n very close to 2 for the resulting oligomers.
22. 15 In eqs 10-13 all free radical species are monomeric, whereas in the companion paper eqs 14-17 deal with long chain-carrying radicals during a polymerization.
23. The temperature was monitored by an external thermocouple on the Peltier temperature controller of the UV-vis spectrometer. However, this thermocouple is not calibrated, and the cell holder is designed for a cell of 1 cm path length, while these experiments required cells of 0.1 or 0.5 cm path length.
24. Gridnev, A. A.; Ittel, S. D.; Fryd, M.; Wayland, B. B. Organometallics 1996, 15, 222-235.
25. (a) Wayland, B. B.; Gridnev, A. A.; Ittel, S. D.; Fryd, M. Inorg. Chem. 1994, 33, 3830-3833.
26. (b) Woska, D. C.; Xie, Z. D.; Gridnev, A. A.; Ittel, S. D.; Fryd, M.; Wayland, B. B. J. Am. Chem. Soc. 1996, 118, 9102-9109.
27. -1.
28. st.
29. st, which may not be accurately measured by UV-vis.
30. Equation 8 suggests that the termination rate constant between dimeric MMA radicals 4 is about 1/3 of that between methylisobutyryl radicals 3.
31. -1 in benzene (at 70°C). See: Bamford, C. H.; Denyer, R.; Hobbs, J. Polymer 1967, 8, 493-496.
32. Also see: Tobolsky, A. V.; Baysal, B. J. Polym. Sci. 1953, 11, 471-486 and references therein.
33. reinit between 5 and MMA at various temperatures were extrapolated from data in Tables 1 and 2 in ref 12.
34. Bizilj, S.; Kelly, D. P.; Serelis, A. K.; Solomon, D. H.; White, K. E. Aust. J. Chem. 1985, 38, 1657-1673.
35. Abramo, G. P.; Norton, J. R. Macromolecules 2000, 33, 2790-2792.
36. Hoobler, R. J.; Hutton, M. A.; Dillard, M. M.; Castellani, M. P.; Rheingold, A. L.; Rieger, A. L.; Rieger, P. H.; Richards, T. C.; Geiger, W. E. Organometallics 1993, 12, 116-123.
37. Cavanagh, J.; Fairbrother, W. J.; Palmer III, A. G.; Skelton, N. J. Protein NMR Spectroscopy Principles and Practice; Academic Press: New York, 1996.
38. 0.