RuCl₂(PPh₃)₃ Catalyzed Hydrosilylation and Dimerization of Phenylacetylene in the Presence of Various Hydrosilanes

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• GC Analysis and Reaction Profiles: The RuCl2(PPh3)3 catalyzed reaction of phenylacetylene with various hydrosilanes in an argon atmosphere was monitored by GC analysis and 1H NMR spectroscopy. In a typical GC experiment, a small (∼ 2mL) reaction flask equipped with a Teflon stopcock (ChemGlass) was charged with phenylacetylene (28 μL, 0.26 mmol), HSiEt3 (42 μ L,0.26 mmol), RuCl2(PPh3)3 (10mg,0.01 mmol,2mol%), mesitylene (20 μ L, internal standard), and benzene (1.0mL) 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 (20 μ L,0.18 mmol), HSiEt3, (29 μ L,0.18 mmol), RuCl2 (PPh3)3 (7mg,0.007 mmol,2mol%), hexamethyldisilane (2 μ L, 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 1H 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.
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