Table 3.

Kinetic data for oxidations of HOArCH₂pyX and HOAr-pyX.

Phenol	Oxidant	Erxn(V)	k (M−1 s−1)	k° (M−1 s−1)a
-CH2pyNMe2	[N(C6H4OMe)3]+•	0.00	5.4 ± 0.5 × 105	5.4 × 105
-CH2pyCH3	[N(C6H4OMe)(C6H4Br)2]+•	0.08	8.0 ± 0.9 × 105	1.7 × 105
	[N(C6H4Me)3]+•	−0.02	1.4 ± 0.2 × 105	2.2 × 105
	[N(C6H4OMe)2(C6H4Br)]+•	−0.08	4.4 ± 0.5 × 104	2.2 × 105
	[Fe(4,7-Me2phen)3]3+	0.13	5.0 ± 0.5 × 105	4.0 × 104
-CH2py	[N(C6H4OMe)(C6H4Br)2]+• b	0.04	5.3 ± 0.5 × 105	2.4 × 105
	[N(C6H4Me)3]+• b	−0.06	1.2 ± 0.1 × 105	3.9 × 105
	[N(C6H4OMe)3]+• b	−0.28	8 ± 2 × 102	1.9 × 105
	[Fe(4,7-Me2phen)3]3+b	0.09	2.5 ± 0.3 × 105	4.3 × 104
CH2pyCF3	[N(C6H4Br)3]+•	0.05	7.5 ± 1.5 × 105	2.8 × 105
	[N(C6H4OMe)(C6H4Br)2]+·	−0.14	7.6 ± 0.8 × 103	1.2 × 105
	[Fe(4,7-Me2phen)3]3+	−0.09	3.4 ± 0.3 × 103	2.0 × 104
-pyCH3	[Fe(5,5′-Me2bpy)3]3+	0.05	2.2 ± 0.2 × 106	8.3 × 105
-py	[Fe(bpy)3]3+ c	0.12	5.2 ± 0.8 × 106	5.0 × 105
	[Fe(5,5′-Me2bpy)3]3+ c	0.00	5.8 ± 0.9 × 105	5.8 × 105
	[Fe(4,4′-Me2bpy)3]3+	−0.07	4.5 ± 0.9 × 105	1.8 × 106
	[Fe(4,7-Me2phen)3]3+ c	−0.05	1.9 ± 0.4 × 106	5.0 × 106
	[Fe(3,4,7,8-Me4phen)3]3+c	−0.12	3.3 ± 0.6 × 105	3.4 × 106
	[Fe(4,4′-tBu2bpy)3]3+	−0.06	4.6 ± 0.5 × 104	1.5 × 105
-pyCF3	[Fe(bpy)3]3+	−0.06	3.7 ± 0.4 × 104	1.2 × 105
	[Fe(phen)3]3+	−0.07	1.6 ± 0.2 × 105	6.3 × 105
-pyNO2	[Fe(bpy)3]3+	−0.09	2.1 ± 0.2 × 104	1.2 × 105
	[Fe(phen)3]3+	−0.10	7.5 ± 1.5 × 104	5.3 × 105

^aIntrinsic rate constants, corrected to ΔG° = 0 (see text).

^bRef. 40.

^cRef. 7.