. Author manuscript; available in PMC: 2010 Mar 4.

Published in final edited form as: Angew Chem Int Ed Engl. 2009;48(7):1291–1295. doi: 10.1002/anie.200804029

Table 1.

Semiclassical KIEs Calculated with DFT (B3LYP/B1)

Reaction ^[a]	KIE(T) ^[b]	KIE(Q) ^[b]	Observed KIE at 40 °C for 1 (2) ^[c]
K_N4Py + C₆H₁₂	6.8	1.9
K_N4Py + PhMe	5.9	1.4	22 (30)
K_N4Py + MeCN	6.7	5.4	(4)
K_N4Py + PhEt	6.3	1.4	45 (40)
K_Bn-TPEN + C₆H₁₂	6.8	2.7	(6)

^[a]

C₆H₁₂ = cyclohexane, PhMe = toluene, MeCN = acetonitrile, PhEt = ethylbenzene. Calculations at the B3LYP/LACVP level. KIEs were calculated using the free energy difference between ^3.5TS_H and ^3,5R (^3,5K_N4Py + substrate). The reacting H atom was replaced by D.

^[b]

Semiclassical values.

^[c]

KIE values determined at 40 °C in MeCN-d₃ solvent, except for MeCN, which was obtained from the t_1/2 values of 2 in MeCN and MeCN-d₃ solvent.