Table 1.

Rate constants for the reactions of 4–12 with peroxyl radicals (k_inh) at 303 K obtained from AIBN-initiated inhibited autoxidations of styrene (50% v/v) in either chlorobenzene (PhCl) or acetonitrile (CH₃CN). O–H Bond dissociation enthalpies calculated using CBS-QB3 are given along with available experimental data where possible.

	kinh (PhCl)		kinh (CH3CN)		kinh (PhCl)/kinh (CH3CN)	BDEOHcalc(exp)a /kcal/mol
	/M−1s−1	n	/M−1s−1	n
4a	(3.6 ± 0.6) × 106 b	1.9	(5.4 ± 0.2) × 105	2.0	7	77.9
4b	(1.4 ± 0.6) × 107 c	1.9	(3.0 ± 0.3) × 106	2.0	5	74.8 (75.9)
4c	(2.0 ± 1.0) × 106 d	2.1	(3.1 ± 0.6) × 105	2.0	6	78.0
4d	(8.5 ± 2.8) × 106 d	1.9	(3.0 ± 0.4) × 106	2.0	3	74.5
5a	(7.3 ± 0.4) × 104	2.2e	(4.1 ± 0.3) × 104	1.9e	18	82.4
5b	(4.4 ± 0.7) × 105 c	2.1	(3.8 ± 0.9) × 104	1.9e	12	78.9
6a	(2.0 ± 0.6) × 106 b	2.1	(3.0 ± 0.7) × 105	1.9	7	78.3
6b	(7.4 ± 0.6) × 106	2.1	(1.0 ± 0.3) × 106	1.8	7	75.6 (77.1)
7a	(3.1 ± 0.4) × 105	2.0	(1.1 ± 0.6) × 104 f	2.1e	28	80.9 (81.4)
7b	(3.7 ± 0.3) × 105	2.0	(1.4 ± 0.5) × 104	2.0e	26	80.9g
8	(4.4 ± 1.0) × 104	2.0e	(1.3 ± 0.5) × 103	n.d.	34	81.8
9a	(5.5 ± 3.1) × 107 h	1.3	(9.2 ± 1.9) × 106	1.7	6	74.9 (75.2i)
9b	(7.8 ± 0.8) × 107 h	1.5	(1.3 ± 0.3) × 107	1.7	6	75.0 (75.2i)
9c	(1.5 ± 0.2) × 107 j	2.0	(2.9 ± 1.4) × 106	2.0	5	75.4
10	(1.1 ± 0.2) × 104 k	2.0e	n.d.	n.d.	-	78.7 (79.9l)
11	(1.1 ± 0.2) × 105 k	2.0	(2.5 ± 1.0) × 104 f	n.d.	4	75.5 (77.2l)
12	(3.2 ± 0.5) × 106 k	2 l	(6.5 ± 0.8) × 105 f	2m	5	77.7 (77.1l)

^aExperimental values (in benzene) obtained by REqEPR at 298 K are from [12–13] and have been corrected for the revised O–H BDE of phenol [19]. ^bValues for 4a and 6a were previously determined as 4.8 × 10⁶ M⁻¹s⁻¹ and 1.1 × 10⁶ M⁻¹s⁻¹ at 303 K from the inhibited oxidation of styrene in PhCl and as 1.1 × 10⁷ M⁻¹s⁻¹ and 6.5 × 10⁶ M⁻¹s⁻¹ at 310 K in benzene by radical clock [16]. ^cValues of 1.6 × 10⁷ M⁻¹s⁻¹ and 2.9 × 10⁵ M⁻¹s⁻¹ were previously reported for 4b and 5b from inhibited styrene oxidation in PhCl at 303 K [14]. ^dValues for 4c and 4d of 3.3 × 10⁶ M⁻¹s⁻¹ and 8.7 × 10⁶ M⁻¹s⁻¹ measured by inhibited autoxidation of styrene in PhCl and of 1.6 × 10⁶ M⁻¹s⁻¹ and 1.4 × 10⁷ M⁻¹s⁻¹ in benzene at 310 K by radical clock [17]. ^eDetermined from the inhibited autoxidation of cumene at 303 K. ^fValues of 7.9 × 10² M⁻¹s⁻¹, 2.2 × 10⁴ M⁻¹s⁻¹ and 6.8 × 10⁵ M⁻¹s⁻¹were previously measured for 7a, 11, 12 from the autoxidation of styrene in acetonitrile at 303 K [20]. ^gAssumed the same as 7a. ^hValues of 6.1 × 10⁷ M⁻¹s⁻¹ and 5.2 × 10⁷ M⁻¹s⁻¹ for 9a and 9b in benzene at 310 K were obtained by radical clock [15]. ⁱMeasured for the analogue of 9a/b with R = R’ = H. ^jThe value of 3.1 × 10⁷ M⁻¹s⁻¹ in benzene at 310 K was obtained by radical clock [15] for an analogue of 9c. ^kValues of 1.4 × 10⁴ M⁻¹s⁻¹, 1.1 × 10⁵ M⁻¹s⁻¹ and 3.8 × 10⁶ M⁻¹s⁻¹ were previously determined for 10, 11 and 12 in the inhibited autoxidation of styrene in PhCl at 303 K [21]. ^lFrom [22]. ^mUsed as reference value.