Table 2.
Comparison of the experimental AE values with the respective calculated threshold values. The threshold energies are calculated for homolytic bond ruptures and where no new bonds are formed the neutral fragments are the radical species.
| m/z | Products | AE (eV) | PBE0-TZVP (eV) | DLPNO-CCSD(T)-TZVP (eV) |
|
| ||||
| 524 | [Au(CH 3 ) 2 Cl] 2 + | 9.4 ± 0.3 | 9.23 | 9.92 |
| 494 | [Au2Cl2(CH3)2]+ + 2CH3 [Au2Cl2(CH3)2]+ + CH3CH3 [Au2Cl2(CH3)2]+ + CH2CH2 + H2 |
9.7 ± 0.2 | 13.51 9.67 11.28 |
14.06 10.29 11.65 |
| 479 | [Au2Cl2(CH3)]+ + 3CH3 [Au2Cl2(CH3)]+ + CH3 + CH3CH3 [Au2Cl2(CH3)]+ + CH2CH2 + H2 + CH3 |
11.4 ± 0.2 | 15.01 11.18 12.78 |
15.04 11.27 12.64 |
| 464 | [Au2Cl2]+ + 4CH3 [Au2Cl2]+ + 2CH3CH3 [Au2Cl2]+ + CH3CH3 + 2CH3 [Au2Cl2]+ + CH2CH2 + H2 + CH3CH3 |
10.1 ± 0.2 | 17.32 9.65 13.48 11.25 |
17.65 10.12 13.89 11.49 |
| 458 | [Au2Cl(CH2CH3)]+ + 2CH3 + Cl + H [Au2Cl(CH2CH3)]+ + CH3CH3 + HCl [Au2Cl(CH2CH3)]+ + CH4 + CH3Cl [Au2Cl(CH2CH3)]+ + CH3CH3 + Cl + H |
10.3 ± 0.2 | 18.72 10.46 10.64 14.88 |
18.50 10.41 10.60 14.73 |
| 444 | [Au2Cl(CH3)]+ + Cl + 3CH3 [Au2Cl(CH3)]+ + Cl + CH3CH3 + CH3 [Au2Cl(CH3)]+ + CH3Cl + 2CH3 [Au2Cl(CH3)]+ + CH3Cl + CH3CH3 |
13.0 ± 0.2 | 17.42 13.58 13.72 9.88 |
17.29 13.52 13.76 9.99 |
| 429 | [Au2Cl]+ + 4CH3 + Cl [Au2Cl]+ + HCl + 2CH4 + CHCH2 [Au2Cl]+ + CH3 + CH3Cl + CH3CH3 [Au2Cl]+ + 2CH3CH3 + Cl |
12.2 ± 0.2 | 19.11 12.54 11.57 11.44 |
18.84 12.33 11.54 11.30 |
| 422 | [Au2(CH2CH2)]+ + 2CH3 + 2Cl + 2H [Au2(CH2CH2)]+ + 2ClCH3 + H2 [Au2(CH2CH2)]+ + CH3CH3 + 2HCl |
10.3 ± 0.3 | 22.20 10.53 9.51 |
21.84 10.46 9.44 |
| 408 | [Au(CH)AuH]+ + 3CH3 + 2Cl + H [Au(CH)AuH]+ + CH2CH2 + 2HCl + CH4 [Au(CH)AuH]+ + CH3CH3 + HCl + ClCH3 |
13.2 ± 0.2 | 24.57 13.35 12.60 |
24.14 13.06 12.54 |
| 394 | [Au2]+ + 4CH3 + 2Cl [Au2]+ + 2CH3 + 2CH3Cl [Au2]+ + CH2CH2 + 2CH3 + 2HCl [Au2]+ + 2CH3CH3 + 2Cl [Au2]+ + 2CH3CH3 + Cl2 [Au2]+ + CH3CH3 + 2CH3Cl |
15.3 ± 0.2 | 22.39 14.99 15.56 14.71 11.99 11.15 |
22.09 15.05 15.39 14.56 12.14 11.28 |
| 227 | [(CH3)Au(CH3)]+ + 2CH3 + 2Cl + Au [(CH3)Au(CH3)]+ + CH3CH3 + Cl2 + Au [(CH3)Au(CH3)]+ + AuCl + CH3CH3 + Cl [(CH3)Au(CH3)]+ + 2CH3Cl + Au [(CH3)Au(CH3)]+ + CH2CH2 + 2HCl + Au |
12.4 ± 0.2 | 17.81 11.24 12.46 10.41 10.98 |
18.72 12.54 12.20 11.68 12.01 |