Table 1.

Activation Gibbs free energies, exothermicity and contribution of alternative pathways (%F) of oxidation of toluene by permanganate anion at several different theory levels (all with IEFPCM)

Attack	ΔG≠ [kcal mol−1]	ΔGR [kcal mol−1]	% F
M05-2X/6-31+G(d,p)
Cm	25.0	−71.9	0.0 (0.0)
C1-C2 a	21.0	−53.9	10.4 (10.4)
C2-C3	19.7	−54.2	86.1 (86.1)
C3-C4	21.6	−52.4	3.5 (3.5)
M05-2X/6-31+G(d,p) with ZPC and thermal corrections
Cm	22.2	−66.6	25.6
C1-C2	22.6	−48.4	12.8
C2-C3	21.8	−48.1	48.2
C3-C4	22.6	−47.0	13.3
M05-2X/aug-cc-pVTZ//M05-2X/6-31+G(d,p) with ZPC and thermal corrections
Cm	18.3	−70.2	99.8
C1-C2	22.5	−50.2	0.1
C2-C3	22.7	−50.3	0.1
C3-C4	26.1	−49.2	0.0
B3LYP/6-31+G(d,p)
Cm	25.9	−25.9	13.1 (16.5)
C1-C2	26.1	−5.8	10.2 (9.8)
C2-C3	25.2	−6.8	43.6 (41.9)
C3-C4	25.4	−6.4	33.1 (31.8)
B3LYP/6-31+G(d,p) with ZPC and thermal corrections
Cm	27.2	−20.2	99.7
C1-C2	32.2	2.4	0.1
C2-C3	30.8	0.9	0.2
C3-C4	33.3	3.4	0.0
B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d,p) with ZPC and thermal corrections
Cm	24.4	−21.0	99.9
C1-C2	33.3	4.0	0.0
C2-C3	32.0	2.6	0.1
C3-C4	34.6	5.0	0.0
Experimental5
Cm			100
Ring oxidation			0

^aFor atom numbering see Fig. 2