Green Chemistry
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ARTICLE
DOI: 10.1039/C6GC00089D
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23 Gas phase basicity (GB) of 2a, calculated at M06ꢀ2X/6ꢀ
311++G(2df,2pd)//M06ꢀ2X/6ꢀ31+G(d,p) level, is 322.8 kcal mol–1, 35 V. Štrukil, M. D. Igrc, L. Fábián, M. EckertꢀMaksić, S. L. Childs, D.
while of ammonia the GB value is 200.0 kcal mol–1. The calculated
G. Reid, M. J. Duer, I. Halasz, C. Mottillo and T. Friščić, Green
Chem. 2012, 14, 2462–2473.
p
Ka values of 2a and ammonia in water are 9.01 and 4.02,
respectively, with SMD/M06ꢀ2X/6ꢀ31+G(d,p)//M06ꢀ2X/6ꢀ31+G(d,p)
approach. While the theoretical prediction of pKa value of ammonia
in water is often compromised due to its small size and high charge
density in the cation (in this case, underestimated by more than 5 pKa
units relative to the experimental value of 9.24), we note the correct
and expected trend in GB values, suggesting ammonia as the most
acidic species in the reaction mixture.
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