Table 1.

The calculated and observed $\mathrm{\Delta }\mathrm{\Delta }{G}_{\mathit{sol}}^{w\to \mathbf{1}}$ for systems explored in this work using three different approaches.^a,^b

Energies	pKaobs	$\mathrm{\Delta }\mathrm{\Delta }{G}_{\mathit{sol},\mathit{obs}}^{w\to \mathbf{1}}$	no ions	$\mathrm{\Delta }\mathrm{\Delta }{G}_{\mathit{sol},\mathit{calc}}^{w\to \mathbf{1}}$ no induced	induced and ions
System
N,N,N′,N′-tetraethyl-1,2-diaminoethane
water	10.8	−4.8	5.7	12.1	−3.8
complex	14.3
TS of triethyl orthoformate
water	no exp.	-	−1.8	4.2	−8.7
complex
TS of triisopropyl orthoformate
water	no exp.	-	2.3	3.4	−7.7
complex

^aEnergies in kcal/mol.

^bThe calculated $\mathrm{\Delta }\mathrm{\Delta }{G}_{\mathit{sol}}^{w\to \mathbf{1}}$ reflects an average over eight conformations (forward and backward) obtained by starting the solvation energy calculations from equally spaced points along the relaxation trajectory. The table also provides the stabilization of the TSs of the reactions studied here. The error range of the calculations is about 2 kcal/mol as judged from the variation of the results obtained by simulations with different starting points.