RuCl2(PPh3)3 catalyzed hydrosilylation and dimerization of phenylacetylene in the presence of various hydrosilanes

Main Group Chemistry

Volumn 3, Issue 2, 2000, Pages 143-147

  Yardy, Nicholas M ^a   Lemke, Frederick R ^a  

^a OHIO UNIVERSITY   (United States)

Author keywords

Hydrosilylation; Phenylacetylene; Ruthenium; Substituent effects

Indexed keywords

EID: 85013582515     PISSN: 10241221     EISSN: 17451167     Source Type: Journal    
DOI: 10.1080/13583140012331339119     Document Type: Article

References (20)

1. Comprehensive Handbook on Hydrosilylation, Marciniec, B. Ed., Pergamon Press: New York, 1992.
2. Ojima, I., In: The Chemistry of Organic Silicon Compounds, Patai, S. and Rappoport, Z. Eds., John Wiley & Sons: New York, NY, 1989, pp. 1479-1526.
3. Ojima, I.; Li, Z.; Zhu, J. In: The Chemistry of Organic Silicon Compounds, Rappoport, Z. and Apeloig, Y. Eds., John Wiley & Sons: New York, NY, 1998, Vol. 2; pp. 1687-1792.
4. Esteruelas, M. A.; Herrero, J.; Oro, L. A. Organometallics 1993, 22, 2377-2379.
5. Atencio, R.; Bohanna, C; Esteruelas, M. A.; Lahoz, F. J.; Oro, L. A. J. Chem. Soc, Dalton Trans. 1995, 2171-2181.
6. Maddock, S. M.; Rickard, C. E. F.; Roper, W. R.; Wright, L. J., Organometallics 1996, 25, 1793-1803.
7. Esteruelas, M. A.; Lopez, A. M.; Oro, L. A.; Tolosa, J. I., J. Mol. Cat. A 1995, 96, 21-23.
8. Watanabe, H.; Asami, M.; Nagai, Y. J. Organomet. Chem. 1980, 195, 363-373.
9. Lemke, F. R. J. Am. Chem. Soc. 1994, 116, 11183-11184.
10. Lemke, F. R.; Chaitheerapapkul, C. Polyhedron 1996, 15, 2559-2565.
11. Lemke, F. R.; Galat, K. J.; Youngs, W. J., Organometallics 1999, 18, 1419-1429.
12. GC Analysis and Reaction Profiles: The RuCl2(PPh3)3 catalyzed reaction of phenylacetylene with various hy-drosilanes in an argon atmosphere was monitored by GC analysis and ‘H NMR spectroscopy. In a typical GC experiment, a small (~2 mL) reaction flask equipped with a Teflon stopcock (ChemGlass) was charged with phenylacetylene (28).iL,0.26 mmol), HSiEt, (42 iL,0.26mmol), RuCl2(PPh3)3 (10mg,0.01mmol,2mol%), mesitylene (20 uL, internal standard), and benzene (l.OmL) under an argon atmosphere. An initial aliquot was taken for GC analysis before placing the reaction tube into a 65°C sand or oil bath. Upon completion of the reaction (~12hr), a second aliquot was taken under an inert atmosphere for GC analysis. Peak areas were normalized to the internal standard and used to calculate the percent consumption of phenylacetylene and the percent yield of the products (Tab. 1). In a typical NMR experiment, a 5 mm NMR tube equipped with a J Young Teflon valve (Wilmad) was charged with phenylacetylene (20nL,0.18mmol), HSiEt3 (29)jL,0.18 mmol), RuCl2(PPh3)3 (7mg,0.007mmol,2mol%), hexamethyldisilane (2\iL, internal standard) and C6D6 (0.75 mL) under an argon atmosphere. After an initial spectrum was collected at room temperature, the NMR probe was heated to and maintained at 65°C for the duration of the experiment. Full ‘H NMR spectra were obtained at regular intervals. Integrated peak areas were normalized with respect to hexamethyldisilane to determine the percent consumption of the reagents and the percent yield of the products.
13. HSiMeCl2 Concentration Effect: In an argon filled glovebox, six 2mL reaction tubes equipped with threaded Teflon valves (ChemGlass) were charged with RuCl2(PPh3)3 (10 mg), mesitylene (40 ĮiL, internal standard), and phenylacetylene (0.20mL). HSiMeCl2 and benzene were added to bring the total solution volume to l.OmL with [HSiMeClJ covering a 0.50-7.68 M range. Samples were mixed and initial sample aliquots (10 jL) was taken. The samples were heated to 65°C for 12hrs and final sample aliquots were taken. The initial and final sample aliquots were diluted in benzene (1 mL) and analyzed by GC. The measured /3-dichloromethylsilylstyrene Z/E ratios ([HSiMeClJ) were 18.3\pm3.8 (7.68 M), 25.1\pm2.7 (4.80 M), 34.8\pm2.9 (2.99M), 46.7\pm3.0 (1.99M), 81.7\pm4.4 (LOOM), and 101.3\pm5.2 (0.50M).
14. Slugovc, C; Mereiter, K.; Zobetz, E.; Schmid, R.; Kirshner, K. Organometallics 1996, 15, 5275-5277.
15. Yi, C. S.; Liu, N. Organometallics 1996, 15, 3968-3971.
16. Yi, C. S.; Liu, N.; Rheingold, A. L.; Liable-Sands, L. M., Organometallics 1997, 16, 3910-3913.
17. Svoboda, P.; Rerichą, R.; Hetflejs, J. Collection Czechosolv. Chem. Commun. 1974, 39, 1324-1329.
18. Kono, H.; Wakao, N.; Ito, K.; Nagai, Y. J. Organomet. Chem. 1977, 232, 53-67.
19. Eaborn, C; Odeli, K.; Pidcock, A. J. Organomet. Chem. 1973, 63, 93-97.
20. Hübler, K.; Hübler, U.; Roper, W. R.; Schwerdtfeger, P.; Wright, L. J. Chem. Eur. J. 1997, 3, 1608-1616.