A theoretical investigation of ruthenium-catalyzed alkene hydrosilation: Evidence to support an exciting new mechanistic proposal

Journal of the American Chemical Society

Volumn 126, Issue 42, 2004, Pages 13564-13565

  Beddie, Chad ^a   Hall, Michael B ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; HYDROGEN; RUTHENIUM;

ARTICLE; CATALYSIS; CHEMICAL INTERACTION; ENERGY; HYDROGEN BOND; HYDROSILYLATION; OXIDATION; REACTION ANALYSIS; THEORY;

EID: 6444224437     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046525z     Document Type: Article

References (21)

1. (a) Tilley, T. D. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley & Sons: New York, 1989; pp 1415-1477.
2. (b) Ojima, I. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley & Sons: New York, 1989; pp 1479-1526.
3. (c) Marciniec, B. Appl. Organomet. Chem. 2000, 14, 527-538 and references therein.
4. Glaser, P. B.; Tilley, T. D. J. Am. Chem. Soc. 2003, 125, 13640-13641.
5. For example, in the Chalk-Harrod mechanism, olefin inserts into the metal-hydrogen bond: (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 16-21. (b) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 1133-1135. In the modified Chalk-Harrod mechanism proposed by Sietz and Wrighton, olefin insens into the metal-silicon bond: (c) Scitz. F.; Wrighton, M. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 289-291. (d) Duckett, S. B.; Perutz, R. N. Organometallics 1992, 11, 90-98. Furthermore, σ-bond metathesis hydrosilation mechanisms that are proposed for d° metals also occur within the first coordination sphere of the transition metal: (e) Corey, J. Y.: Zhu, X.-H. Organometallics 1992, 11, 672-683. (f) Kesti, M. R.; Waymouth, R. M. Organometallics 1992, 11, 1095-1103.
6. For example, in the Chalk-Harrod mechanism, olefin inserts into the metal-hydrogen bond: (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 16-21. (b) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 1133-1135. In the modified Chalk-Harrod mechanism proposed by Sietz and Wrighton, olefin insens into the metal-silicon bond: (c) Scitz. F.; Wrighton, M. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 289-291. (d) Duckett, S. B.; Perutz, R. N. Organometallics 1992, 11, 90-98. Furthermore, σ-bond metathesis hydrosilation mechanisms that are proposed for d° metals also occur within the first coordination sphere of the transition metal: (e) Corey, J. Y.: Zhu, X.-H. Organometallics 1992, 11, 672-683. (f) Kesti, M. R.; Waymouth, R. M. Organometallics 1992, 11, 1095-1103.
7. For example, in the Chalk-Harrod mechanism, olefin inserts into the metal-hydrogen bond: (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 16-21. (b) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 1133-1135. In the modified Chalk-Harrod mechanism proposed by Sietz and Wrighton, olefin insens into the metal-silicon bond: (c) Scitz. F.; Wrighton, M. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 289-291. (d) Duckett, S. B.; Perutz, R. N. Organometallics 1992, 11, 90-98. Furthermore, σ-bond metathesis hydrosilation mechanisms that are proposed for d° metals also occur within the first coordination sphere of the transition metal: (e) Corey, J. Y.: Zhu, X.-H. Organometallics 1992, 11, 672-683. (f) Kesti, M. R.; Waymouth, R. M. Organometallics 1992, 11, 1095-1103.
8. For example, in the Chalk-Harrod mechanism, olefin inserts into the metal-hydrogen bond: (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 16-21. (b) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 1133-1135. In the modified Chalk-Harrod mechanism proposed by Sietz and Wrighton, olefin insens into the metal-silicon bond: (c) Scitz. F.; Wrighton, M. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 289-291. (d) Duckett, S. B.; Perutz, R. N. Organometallics 1992, 11, 90-98. Furthermore, σ-bond metathesis hydrosilation mechanisms that are proposed for d° metals also occur within the first coordination sphere of the transition metal: (e) Corey, J. Y.: Zhu, X.-H. Organometallics 1992, 11, 672-683. (f) Kesti, M. R.; Waymouth, R. M. Organometallics 1992, 11, 1095-1103.
9. For example, in the Chalk-Harrod mechanism, olefin inserts into the metal-hydrogen bond: (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 16-21. (b) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 1133-1135. In the modified Chalk-Harrod mechanism proposed by Sietz and Wrighton, olefin insens into the metal-silicon bond: (c) Scitz. F.; Wrighton, M. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 289-291. (d) Duckett, S. B.; Perutz, R. N. Organometallics 1992, 11, 90-98. Furthermore, σ-bond metathesis hydrosilation mechanisms that are proposed for d° metals also occur within the first coordination sphere of the transition metal: (e) Corey, J. Y.: Zhu, X.-H. Organometallics 1992, 11, 672-683. (f) Kesti, M. R.; Waymouth, R. M. Organometallics 1992, 11, 1095-1103.
10. For example, in the Chalk-Harrod mechanism, olefin inserts into the metal-hydrogen bond: (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 16-21. (b) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87, 1133-1135. In the modified Chalk-Harrod mechanism proposed by Sietz and Wrighton, olefin insens into the metal-silicon bond: (c) Scitz. F.; Wrighton, M. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 289-291. (d) Duckett, S. B.; Perutz, R. N. Organometallics 1992, 11, 90-98. Furthermore, σ-bond metathesis hydrosilation mechanisms that are proposed for d° metals also occur within the first coordination sphere of the transition metal: (e) Corey, J. Y.: Zhu, X.-H. Organometallics 1992, 11, 672-683. (f) Kesti, M. R.; Waymouth, R. M. Organometallics 1992, 11, 1095-1103.
11. Brunner, H. Angew. Chem., Int. Ed. 2004, 43, 2749-2750.
12. For theoretical investigations on other hydrosilation catalysts, see: (a) Sakaki, S.; Takayama, T.; Sumimoto, M.; Sugimoto, M. J. Am. Chem. Soc. 2004, 126, 3332-3348. (b) Chung, L. A.; Wu, Y.; Trost, B. M.; Ball, Z. T. J. Am. Chem. Soc. 2003, 125, 11578-11582. (c) Sakaki, S.; Sumimoto, M.; Fukuhara, M.: Sugimoto, M.; Fujimoto, H.; Matsuzaki, S. Organometallics 2002, 21, 3788-3802 and references therein.
13. For theoretical investigations on other hydrosilation catalysts, see: (a) Sakaki, S.; Takayama, T.; Sumimoto, M.; Sugimoto, M. J. Am. Chem. Soc. 2004, 126, 3332-3348. (b) Chung, L. A.; Wu, Y.; Trost, B. M.; Ball, Z. T. J. Am. Chem. Soc. 2003, 125, 11578-11582. (c) Sakaki, S.; Sumimoto, M.; Fukuhara, M.: Sugimoto, M.; Fujimoto, H.; Matsuzaki, S. Organometallics 2002, 21, 3788-3802 and references therein.
14. For theoretical investigations on other hydrosilation catalysts, see: (a) Sakaki, S.; Takayama, T.; Sumimoto, M.; Sugimoto, M. J. Am. Chem. Soc. 2004, 126, 3332-3348. (b) Chung, L. A.; Wu, Y.; Trost, B. M.; Ball, Z. T. J. Am. Chem. Soc. 2003, 125, 11578-11582. (c) Sakaki, S.; Sumimoto, M.; Fukuhara, M.: Sugimoto, M.; Fujimoto, H.; Matsuzaki, S. Organometallics 2002, 21, 3788-3802 and references therein.
15. All calculations were conducted using the Gaussian03 suite of programs: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.: Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada. M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.: Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.: Al-Laham. M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.: Gonzalez, C.; Pople, J. A. Gaussian 03, revision B.4; Gaussian, Inc.: Pittsburgh, PA, 2003.
16. 4, respectively, to save computational time.
17. All relative free energies were calculated in the gas phase with complex 1 and separated ethylene set to 0.0 kcal/mol unless otherwise noted.
18. CPCM calculations employing dichloromethane as a solvent. See the Supporting Information for more details.
19. See Scheme S2 in the Supporting Information for more details.
20. Separate Chalk-Harrod and modified Chalk-Harrod mechanisms that involve σ-bond metathesis steps that couple C-H and C-Si bond formation with Si-H oxidation were also identified; these pathways demonstrated even higher overall barriers to hydrosilation and are illustrated in the Supporting information.
21. See Scheme S9 in the Supporting Information for more details.