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Reaction of Trimethylsilylacetylenes with Antimony Pentafluoride under Matrix Isolation Conditions: Experimental and Computational Study

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journal contribution
posted on 15.10.2010, 00:00 by Helena Čičak, Hrvoj Vančik, Zlatko Mihalić
Reaction of trimethylsilylacetylenes Me3SiCCR with SbF5 in the solid state was investigated using matrix isolation infrared spectroscopy and quantum-mechanical calculations. Two reaction pathways were detected. Replacement of the trimethylsilyl group with SbF4 produces neutral antimony acetylides F4SbCCR. Acetylenic bond protonation produces silyl cation 6-R, fully bridged for R = H and SiMe3. High total charges on the bridging SiMe3 group and low Me3Si−C bond orders to acetylenic moiety, both calculated at the MP4(SDQ)/6-311G(d,p) level of theory, indicate high silyl cation character of these species.