Table 2. Calculated BDE(N–H), IE, and PA (kcal/mol) Values of PhozNH and PhtzNH Derivatives at the M05-2X/6-311++G(d,p) + ZPE Levela.
| PhozNHs (X = O) |
PhtzNHs (X = S) |
|||||
|---|---|---|---|---|---|---|
| substituent Y | BDE(N–H) | IE | PA | BDE(N–H) | IE | PA |
| H | 76.7a(0.0) | 159.8(0.0) | 343.8(0.0) | 80.6b(0.0) | 158.4f(0.0) | 345.1(0.0) |
| F | 75.3(−1.4) | 165.3(5.5) | 338.2(−5.6) | 79.2(−1.4) | 164.6(6.2) | 339.4(−5.7) |
| Cl | 76.2(−0.5) | 165.3(5.5) | 333.8(−10.0) | 80.1c(−0.5) | 164.6(6.2) | 335.5(−9.6) |
| CH3 | 75.2(−1.5) | 153.2(−6.6) | 345.7(1.9) | 78.9(−1.7) | 152.5(−5.9) | 347.3(2.2) |
| OCH3 | 72.9d(−3.8) | 148.3(−11.5) | 346.9(3.1) | 76.5d(−4.1) | 148.8(−9.6) | 347.8(2.7) |
| NH2 | 70.7(−6.0) | 138.8(−21.0) | 350.7(6.9) | 75.0(5.6) | 140.3(−18.1) | 351.8(6.7) |
| CF3 | 79.3(2.6) | 176.9(17.1) | 323.8(−20.0) | 82.5(1.9) | 174.2(14.8) | 325.6(−19.5) |
| CN | 79.4(2.7) | 181.3(21.5) | 317.2(−26.6) | 82.3(1.7) | 178.6(20.2) | 319.1(−26.0) |
| NO2 | 80.4(3.7) | 186.0(26.2) | 310.7(−33.1) | 83.2e(2.6) | 182.5(24.1) | 313.1(−32.0) |
a
In benzene: a77.6; b81.7; c81.6; d77.3; and e85.3 kcal/mol in this work; a77.2 ± 0.3; b79.3 ± 0.3; c79.8 ± 0.3, d76.3 ± 0.4, and e81.6 ± 1.0 kcal/mol from ref (20) In DMSO: a79.5 and b83.7 kcal/mol in this work and a79.7 and b82.3 kcal/mol from ref (21)f155.4 ± 1.6 kcal/mol (6.73 ± 1.6 eV) and 158.4 kcal/mol (6.87eV) ref (24) Values in parentheses are the differences between the calculated values of substituted derivatives with respect to the parent compounds.