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. Author manuscript; available in PMC: 2020 May 21.
Published in final edited form as: J Am Chem Soc. 2019 Jun 27;141(27):10777–10787. doi: 10.1021/jacs.9b04303

Table 3.

Changes in Thermodynamic Parameters with Substituent for Substituted Fluorenyl-benzoates, from Experiment and DFT Calculationsa

R pKa(CO2H) expt ΔpKa(CO2H) expt ΔBDFECH(CO2−)b (kcal mol−1)
NH2 22.0 +0.8 −0.06
OMe 21.5 +0.3 0.22
H 21.2 0 0
CF3 20.3 −0.9 0.83
a

Relative values are versus the R = H compound.

b

Differences in the DFT-computed bond dissociation free energies (BDFEs) for the carboxylate fluorenyl C–H bond (B3LYP/def2-TZVP with PCM = MeCN).