Table 3.
Comparison of calculated bond lengths and selected angles for substrates, transition states and products of the studied azanone reactions with MeS− or MeSH
| Bond length (Å) | Angle (°) | |||||
|---|---|---|---|---|---|---|
| C-S | S-N | N-O | H-C-S | C-S-N | S-N-O | |
| MeS— + HNO → MeSNHO— | ||||||
| HNO | ||||||
| HF | – | – | 1.168 | |||
| M06-2X | – | – | 1.192 | |||
| B2PLYP-D3 | – | – | 1.210 | |||
| B3LYP-D3 | – | – | 1.201 | |||
| MeS– | ||||||
| HF | 1.833 | – | – | |||
| M06-2X | 1.836 | – | – | |||
| B2PLYP-D3 | 1.842 | – | – | |||
| B3LYP-D3 | 1.849 | – | – | |||
| TS | ||||||
| HF | 1.808 | 2.139 | 1.261 | 110.58 | 99.35 | 111.34 |
| M06-2X | 1.796 | 2.198 | 1.275 | 111.39 | 94.77 | 110.23 |
| B2PLYP-D3 | 1.804 | 1.999 | 1.336 | 110.71 | 97.26 | 111.69 |
| B3LYP-D3 | 1.812 | 2.017 | 1.329 | 110.56 | 98.46 | 111.99 |
| MeSHNO– | ||||||
| HF | 1.807 | 1.691 | 1.383 | 106.79 | 106.16 | 115.25 |
| M06-2X | 1.812 | 1.726 | 1.391 | 107.77 | 104.01 | 114.19 |
| B2PLYP-D3 | 1.820 | 1.749 | 1.404 | 107.62 | 104.86 | 114.54 |
| B3LYP-D3 | 1.830 | 1.762 | 1.396 | 107.40 | 105.96 | 115.19 |
| MeSH + HNO → MeSNHOH | ||||||
| HNO | ||||||
| HF | – | – | 1.168 | |||
| M06-2X | – | – | 1.192 | |||
| B2PLYP-D3 | – | – | 1.210 | |||
| B3LYP-D3 | – | – | 1.201 | |||
| MeSH | ||||||
| HF | 1.815 | – | – | |||
| M06-2X | 1.816 | – | – | |||
| B2PLYP-D3 | 1.823 | – | – | |||
| B3LYP-D3 | 1.829 | – | – | |||
| TS | ||||||
| HF | 1.792 | 1.686 | 1.408 | 108.36 | 102.60 | 99.08 |
| M06-2X | 1.791 | 1.708 | 1.411 | 107.28 | 99.90 | 100.12 |
| B2PLYP-D3 | 1.796 | 1.723 | 1.429 | 108.72 | 100.19 | 99.87 |
| B3LYP-D3 | 1.805 | 1.728 | 1.427 | 108.16 | 100.67 | 99.95 |
| MeSNHOH | ||||||
| HF | 1.805 | 1.681 | 1.385 | 105.75 | 105.37 | 115.94 |
| M06-2X | 1.809 | 1.693 | 1.412 | 105.89 | 104.24 | 114.99 |
| B2PLYP-D3 | 1.816 | 1.699 | 1.435 | 105.64 | 105.26 | 115.21 |
| B3LYP-D3 | 1.824 | 1.702 | 1.435 | 105.45 | 106.01 | 115.84 |