. 2014 Jun 27;111(28):10067–10072. doi: 10.1073/pnas.1405065111

Table 1.

Relative Gibbs free energies (Gibbs+E_disp) of species involved in the autocatalyzed by HCl anisole–Cl₂ reaction at B3LYP/6-311+G(2d,2p), PBE/6-311+G(2d,2p), and RB2PLYP/6-311+G(2d,2p)//RB3LYP/6-311+G(2d,2p) and for the uncatalyzed reaction at RB2PLYP/6-311+G(2d,2p)

Species	Description	B3LYP^*, kcal/mol, catalyzed, gas phase	B3LYP^*, kcal/mol, catalyzed, CCl₄	PBEPBE^*, kcal/mol, catalyzed, CCl₄	B2PLYP//B3LYP^*, kcal/mol, catalyzed, CCl₄	B2PLYP^†, kcal/mol, uncatalyzed, CCl₄
π-ortho		2.63	2.81	1.20	2.98	2.99
π-para		2.76	2.86	1.53	3.26	3.23
TS1	o substitution	32.19	22.24	15.97	23.71	—
TS2	m substitution	39.65	32.14	25.09	34.58	—
TS3	p substitution	30.84	20.99^‡	14.96	22.56^§	—
TS4	2,3 addition	32.97 cis add.	21.00 trans add.	17.72 cis add.	22.08 trans add.	34.75 cis add.
TS4_meta^¶	2,3 addition	39.19 cis add.	30.51 trans add.	24.58 trans add.	32.31 trans add.	—
TS5	3,4-cis addition	30.07	17.78	13.15	18.93	30.65
TS5_meta^¶	3,4-cis addition	40.61	31.73	25.26	33.85	—
TS6	2,3-cis–trans	29.24	—	14.66	—	—
TS7	3,4-cis–trans	25.48	14.49^§	11.73^§	14.80^§	21.21
TS7_meta^¶	3,4-cis–trans	35.11	26.96	22.78	28.15	—
TS8	2,3-cis HCl eli.	17.15	10.44	6.35	11.51	16.85
TS8_meta^¶	2,3 HCl eli.	35.56 trans eli.	20.13 cis eli.	14.05 cis eli.	21.55 cis eli.	25.86 cis eli.
TS9	3,4-cis HCl eli.	13.27	6.60	3.36	7.43	12.73
TS9_meta^¶	3,4-cis HCl eli.	23.31	19.83	13.41	21.49	24.73
TS10	cis–cis rot.	—	10.61	8.20	7.73	5.21
TS11	trans–trans rot.	7.48	8.08	5.36	5.65	2.20
P1	o product	−21.45	−21.52	−22.75	−24.16	−27.47
P2	m product	−23.35	−22.80	−23.46	−25.26	−28.37
P3	p product	−23.47	−23.63	−23.21	−26.08	−28.28
P4	2,3-cis adduct	7.60	—	3.15	—	—
P5′	3,4-cis adduct	—	5.50	1.01	2.50	−0.42
P5′′	3,4-cis adduct	8.47	8.26	4.47	5.57	3.01
P5_meta^‖	3,4-cis adduct	6.05	7.08	3.52	3.81	—
P6	2,3-trans adduct	2.10	2.42	−1.02	−0.33	−3.36
P6_meta^‖	2,3-trans adduct	—	6.12	2.56	3.69	—
P7′	3,4-trans adduct	1.15	1.53	−0.32	−0.89	0.09
P7′′	3,4-trans adduct	5.11	5.18	2.06	3.09	−3.54
P7_meta^‖	3,4-trans adduct	2.00	2.31	−0.69	−0.28	—

rot., rotation; eli., elimination; add., addition.

Energies are relative to anisole, Cl₂, and HCl, except for the π-complexes, where the energies are relative to anisole and Cl₂.

^{^†}

Only data for stable wave functions obtained for the uncatalyzed chlorination are shown in this column (see text for additional explanations). Energies are relative to anisole and Cl₂.

^{^‡}

From B3LYP/6-311+G(2d,2p)//B3LYP/6-31+G(d,p) computations.

^{^§}

Δ(G+E_disp) was determined from IEF-PCM (integral equation formalism of the polarizable continuum model) single-point computations at the gas-phase optimized structure.

^{^¶}

High-energy transition states, leading to formation of adducts, in which the orientation of the HCl leads to formation of m-substituted product;

^{^‖}

High-energy adducts, leading to m-substituted product formation.