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Standard operating conditions: P(He) = 0.40 Torr, ν(He) = 9400 cm/s, F(He) = 190STPcm3/s, T= 298 K; cf.
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Similar structural features are computed for CH2Cl− and CH2F− at lower levels of theory; cf.: Schleyer, P. v. R.; Clark, T.; Kos, A. J.; Spitznagel, G. W.; Rohde, C.; Arad, D.; Houk, K. N.; Rondan, N. G. J. Am. Chem. Soc. 1984, 106, 6467. Reoptimization of the geometry of CF2Cl− at the MP2-(full)/6-31+G(d) level yields a more “carbanion-like” geometry with a 2.0-Å C–Cl bond and a reduced negative charge on Cl. However, a substantial basis set superposition error (BSSE) is indicated by counterpoise calculations. The true geometry for CF2Cl− probably lies somewhere between these two extremes.
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Similar structural features are computed for CH2Cl− and CH2F− at lower levels of theory; cf.: Schleyer, P. v. R.; Clark, T.; Kos, A. J.; Spitznagel, G. W.; Rohde, C.; Arad, D.; Houk, K. N.; Rondan, N. G. J. Am. Chem. Soc. 1984, 106, 6467. Reoptimization of the geometry of CF2Cl− at the MP2-(full)/6-31+G(d) level yields a more “carbanion-like” geometry with a 2.0-Å C–Cl bond and a reduced negative charge on Cl. However, a substantial basis set superposition error (BSSE) is indicated by counterpoise calculations. The true geometry for CF2Cl− probably lies somewhere between these two extremes.
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CS2 was used instead of CO2 for these experiments because of the nominal mass overlap between CH3OCHCl− and CO2Cl−.
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