. Author manuscript; available in PMC: 2011 Mar 17.

Published in final edited form as: J Am Chem Soc. 2010 Mar 17;132(10):3304–3311. doi: 10.1021/ja903653j

Table 2.

Predicted solvent-corrected (CPCM) free energy barriers (ΔG^‡, 423K) free energy barrier differences [ΔΔG^‡ = ΔG^‡(TS3) - ΔG^‡(TS2)] along with experimentally measured 2:3 ratios and corresponding ΔΔG^‡ values. All energies given in kcal mol⁻¹.^a

Product		M05-2X		M06-2X		B3LYP		Experiment

		ΔG^‡	ΔΔG^‡	ΔG^‡	ΔΔG^‡	ΔG^‡	ΔΔG^‡	2:3 Ratio	ΔΔG^‡
H	2a	38.1		37.4		58.5		-	-
Me	2b	36.7		35.4		60.5
	3b	36.7	0.0	36.1	0.3	59.8	−0.7	1:3	−0.9
OMe	2c	37.1		36.2		61.0
	3c	38.9	1.8	38.2	2.0	60.8	−0.2	5:1	1.4
Br	2d	33.1		32.6		60.8
	3d	34.4	1.3	34.2	1.7	60.6	−0.2	17:1	2.4
C	2e	28.4		27.5		58.9
	3e	30.6	2.2	29.9	2.4	59.8	0.9	^b	^b
F	2f	35.4		34.9		58.3
	3f	38.4	2.9	37.8	2.9	59.0	0.7	^b	^b

AVDZ′ basis set used for substrates 2d and 3d. 6-31+G(d) basis set used for the remaining systems.

Substrates 1e and 1f were not tested experimentally.