Conclusions
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1.
The geometry, energy and electronic characteristics were calculated for ketene, dimethylketene, and hexafluorodimethylketene. Substituent effects on the electronic structure of the cumulene group C=C=O were elucidated and approaches were developed for activation of the reactions of hexafluorodimethylketene with sulfur chlorides and sulfenyl chlorides by specific solvation of the reagents.
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2.
A necessary condition for the reactions of hexafluorodimethylketene with sulfur chlorides and sulfenyl chlorides is specific solvation of the S-Cl bond of the sulfur chlorides and sulfenyl chlorides. The solvent activating effects are enhanced with increasing donor properties of such solvents.
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3.
Experimental evidence was found supporting the proposed mechanism for the reactions of hexafluorodimethylketene with sulfur chlorides and sulfenyl chlorides.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1371–1378, June, 1984.
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Shkurak, S.N., Ezhov, V.V., Kolomiets, A.F. et al. Activated addition of sulfur chlorides and sulfenyl chlorides to hexafluorodimethylketene. Russ Chem Bull 33, 1261–1268 (1984). https://doi.org/10.1007/BF00948999
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DOI: https://doi.org/10.1007/BF00948999