Table 3.
Bond dissociation enthalpy (BDE) scale (XO → X + 3O) and (reverse) transfer thermodynamic reactivity scale (−TTRS: XO → X + ½ O2) (simply the reverse of the scale in Table 19 of reference [14]). All values are in kcal/mol. See Supplemental Information for Kekulé Structures.
| XO (Oxide of Amine, Amide or Other) | BDE (XO → X + 3O) | −TTRS (XO → X + ½ O2) | ||||
|---|---|---|---|---|---|---|
| Exp’t | B3LYP/6-31G* | M06/6-311G+(d,p) | Exp’t | B3LYP/6-31G* | M06/6-311G+(d,p) | |
| CO2 (Carbon dioxide) | 127.3 | 129.5 | 134.9 | 67.7 | 67.8 | 77.8 |
| NO2 (Nitrogen dioxide) | 73.5 | 75.9 | 76.0 | 13.9 | 14.2 | 18.9 |
| 1-Aza-1,3-cyclohexadiene N-oxide a | - | 69.2 | 68.7 | - | 7.5 | 11.6 |
| 1-Azacyclohexene N-oxide a | - | 65.9 | 66.0 | - | 4.2 | 8.9 |
| 2-Carboxylpyridine N-oxide | 65.9 | 64.3 | 62.0 | 6.3 | 2.6 | 4.9 |
| 4-Cyanopyridine N-oxide | 63.5 | 63.1 | 62.1 | 3.9 | 1.4 | 5.0 |
| Pyridine N-oxide (PNO) | 63.4 | 62.1 | 61.5 | 3.8 | 0.4 | 4.4 |
| 3-Cyanopyridine N-oxide | 60.8 | 59.7 | 58.9 | 1.2 | −2.0 | 1.8 |
| 1-Azabicyclo[2.2.2]octane N-oxide (Quinuclidine-N-oxide) |
- | 52.8 | 55.7 | - | −8.9 | −1.4 |
| 1-Azaadamantane-2-one N-oxide a | - | 48.8 | 50.3 | - | −12.9 | -6.8 |
| Trimethylamine N-oxide (TMAO) | 61.1 b | 48.6 | 51.5 | 1.5 b | −13.1 | −5.6 |
| 1-Azabicyclo[3.3.2]decane N-oxide a | - | 48.2 | 50.2 | - | −13.5 | −6.9 |
| 1-Azabicyclo[2.2.2]octan-2-one N-oxide a (2-Quinuclidinone N-oxide) |
- | 47.7 | 49.6 | - | −14.1 | −7.5 |
| 1-Azabicyclo[3.3.3]undecane N-oxide a (Manxine N-oxide) |
- | 46.3 | 47.2 | - | −15.4 | −9.9 |
| 1-Azabicyclo[4.3.3]dodecane N-oxide a | - | 39.3 | 40.4 | - | −22.4 | −16.7 |
| 1-Azabicyclo[3.3.1]nonan-2-one N-oxide a | - | 37.2 | 38.8 | - | −24.6 | −28.3 |
| N-Methyl-2-pyrrolidinone N-oxide a | - | 34.6 | 35.8 | - | −27.1 | −21.3 |
| 1-Azabicyclo[3.3.3]undecane-2-one N-oxide a (2-Manxinone N-oxide) |
- | 29.9 | 31.4 | - | −31.8 | −25.7 |
a Compound presently unknown. b See further discussion in text.