Table 1. Comparison of Thermochemical Parameters Calculated at the M05-2X/6-311++G(d,p) Level and the Experiment for Selected N–H Compounds (kcal/mol)a,b.
| BDE(N–H)c |
IE |
PA |
||||
|---|---|---|---|---|---|---|
| compounds | calc. | exptl.d | calc. | exptl.e | calc. | exptl.e |
| NH3 | 107.3(−0.9) | 108.2 ± 0.3 | 234.3(2.1) | 232.2 ± 0.5 | 404.3(0.9) | 403.4 ± 1.2 |
| CH3NH2 | 99.2(−2.4) | 101.6 ± 2.0 | 207.1(3.3) | 205.2 ± 2.3 | 402.9(0.9) | 402.0 ± 2.6 |
| (CH3)2NH | 93.7(0.4) | 94.1 | 190.3(0.3) | 190.0 ± 1.8 | 394.9(−0.2) | 395.1 ± 2.0 |
| NH2CN | 99.9(0.2) | 99.0 | 244.2(−1.2) | 245.4 | 345.0(−4.2) | 349.2 ± 2.9 |
| C6H5NH2 | 95.0(2.7/5.3) | 92.3/89.7 | 177.2(−0.7) | 178.0 ± 0.05 | 366.1(−2.1) | 368.0 ± 0.3 |
| 4F–C6H4NH2 | 93.9(5.1) | 88.8 | 179.2(−3.2) | 182.2 ± 2.3 | 362.8(−1.4) | 364.2 ± 2.1 |
| 4Me–C6H4NH2 | 93.1(5.6) | 87.5 | 170.6(0.6) | 170.0 ± 0.5 | 366.1(−0.8) | 366.9 ± 2.1 |
| 4CN–C6H4NH2 | 98.1(2.0) | 95.2 | 195.0(−3.2) | 199.2.0 ± 0.9 | 351.2(2.5) | 348.7 ± 2.1 |
| (C6H5)2NH | 88.5(1.3) | 87.2 | 168.3(2.5) | 165.8 ± 0.3 | 349.4(−0.5) | 350.9 ± 1.3 |
a
Differences between both values are in parentheses.
b
σBDE = 2.6 kcal/mol, σIE = 2.4 kcal/mol, and σPA = 1.9 kcal/mol.
c
Restricted open shell (RO) for open-shell radicals is applied to calculate BDEs.
d
Data taken from ref (18)
e
Data taken from ref (19) (https://webbook.nist.gov/chemistry/).