. Author manuscript; available in PMC: 2010 Aug 26.

Published in final edited form as: J Am Chem Soc. 2009 Aug 26;131(33):11985–11997. doi: 10.1021/ja904400d

Table 1.

Thermodynamic Parameters for Pseudo Self-Exchange Reactions of Nitroxyl Radicals and Hydroxylamines.^a

Reaction	Solvent	K (298 K)	ΔH°	ΔS°
(2) 4-oxo-TEMPO^• + TEMPO-H	CD₃CN	4.5 ± 1.8	−1.7 ± 0.7	−2.6 ± 2.1
4-oxo-TEMPO^• + TEMPO-D	CD₃CN	4.7 ± 1.8	−1.7 ± 0.7	−2.5 ± 2.4
4-oxo-TEMPO^• + TEMPO-H	CD₂Cl₂	7.6 ± 2.4	−2.6 ± 0.8	−4.8 ± 2.6
4-oxo-TEMPO^• + TEMPO-D	CD₂Cl₂	6.6 ± 2.2	−2.6 ± 0.8	−5.1 ± 2.8
(3) 4-oxo-TEMPO^• + 4-MeO-TEMPO-H	CD₃CN	2.8 ± 1.2	−2.2 ± 0.4	−5.8 ± 2.3
4-oxo-TEMPO^• + 4-MeO-TEMPO-D	CD₃CN	3.1 ± 1.2	−2.4 ± 0.7	−5.8 ± 2.3
(4) ^tBu₂NO^• + TEMPO-H	CD₃CN	0.11 ± 0.02	2.7 ± 0.9	4.6 ± 2.8
^tBu₂NO^• + TEMPO-D	CD₃CN	0.11 ± 0.03	2.4 ± 0.9	3.7 ± 2.9
^tBu₂NO^• + TEMPO-H	CD₂Cl₂	0.10 ± 0.02	3.1 ± 0.8	5.6 ± 2.6
^tBu₂NO^• + TEMPO-D	CD₂Cl₂	0.10 ± 0.02	3.1 ± 0.8	5.8 ± 2.4

Measurements at 278−318 K; ΔH° in kcal mol⁻¹, ΔS° in cal mol⁻¹ K⁻¹.