Supplemantary Material
A Theoretical Study of 1,3-Dipolar Cycloadditions of Nitrone and Fulminic Acid with Substituted
Ethylenes
Figure 3. Nitrone/Vinylamine Transition State Geometries
2.185 2.166
1.378 1.386 1.306 1.338
1.294 1.296
2.097 2.298
2.133 2.165
1.383 1.386 1.305 1.334
1.303 1.299
2.227 2.349
1.287 1.299
2.043 2.096
1.374 1.390 2.164
2.171
1.310 1.341
1.313 1.345 2.156
2.173
1.284 1.294
2.090 2.162
1.374 1.388 E(RHF)=100.35 kJ/mol
E(B3LYP)=51.17 kJ/mol
E(RHF)=113.13 kJ/mol E(B3LYP)=40.54 kJ/mol
E(RHF)=149.46 kJ/mol E(B3LYP)=81.42 kJ/mol
Figure 4. Nitrone/Acrylonitrile Transition State Geometries
1.381 1.391 2.149
2.130
1.312 1.339
1.274 1.279
2.050 2.272
1.380 1.391 2.133
2.103
1.312 1.340
1.274 1.273
2.065 2.309
1.394 1.399 2.360
2.299
1.291 1.327
1.294 1.327
1.866 1.982
1.396 1.401 2.380
2.315
1.290 1.326
1.295 1.302
1.849 1.962 E(RHF)=113.13 kJ/mol
E(B3LYP)=35.23 kJ/mol
E(RHF)=117.57 kJ/mol E(B3LYP)=38.96 kJ/mol
E(RHF)=92.29 kJ/mol E(B3LYP)=38.89 kJ/mol
Figure 5. Nitrone/Acrolein (s-cis) Transition State Geometries
1.378 1.382 2.084
2.157
1.317 1.33
1.273 1.275
2.131 2.402
1.377 1.387 2.091
2.077
1.315 1.340
1.279 1.277
2.111 2.384
1.409 1.401 2.490
2.377
1.280 1.321
1.300 1.305
1.779 1.928
1.407 1.400 2.556
2.433 1.276 1.317
1.298 1.303
1.784 1.931 E(RHF)=87.62 kJ/mol
E(B3LYP)=5.03 kJ/mol
E(RHF)=103.88 kJ/mol E(B3LYP)=24.45 kJ/mol
E(RHF)=82.89 kJ/mol E(B3LYP)=29.68 kJ/mol
Figure 6. Nitrone/Acrolein (s-trans) Transition State Geometries
1.379 1.386 2.132
2.125
1.311 1.338
1.279 1.279
2.087 2.321
1.380 1.389 2.144
2.117
1.311 1.340
1.278 1.279
2.073 2.298
1.394 1.398 2.354
2.309
1.293 1.327
1.295 1.302
1.877 1.982
1.395 1.399 2.359
2.314
1.293 1.327
1.295 1.303
1.867 1.966 E(RHF)=115.42 kJ/mol
E(B3LYP)=36.94 kJ/mol
E(RHF)=117.41 kJ/mol E(B3LYP)=41.10 kJ/mol
E(RHF)=96.71 kJ/mol E(B3LYP)=38.43 kJ/mol
Figure 7. Fulminic Acid/Propene Transition State Geometries
1(R)
1 2
3
2(R)
1.364 1.369 2.145
2.224
1.178 1.210
1.229 1.225
2.310 2.477
1.364 1.371 2.146
2.223
1.179 1.212
1.227 1.225
2.254 2.396
E(RHF)=135.64 kJ/mol E(B3LYP)=50.41 kJ/mol
Figure 8. Fulminic Acid/Vinylamine Transition State Geometries
1(R)
1 2
3
2(R)
E(RHF)=110.38 kJ/mol E(B3LYP)=36.87 kJ/mol
E(RHF)=165.99 kJ/mol E(B3LYP)=77.48 kJ/mol 1.368
1.371 2.145
2.251
1.179 1.208
1.242 1.232
2.579 2.719
1.364 1.377 2.108
2.168
1.181 1.218
1.232 1.233
Figure 9. Fulminic Acid/Acrylonitrile Transition State Geometries
1(R)
1 2
3
2(R)
E(RHF)=146.34 kJ/mol E(B3LYP)=46.59 kJ/mol
E(RHF)=135.83 kJ/mol E(B3LYP)=54.85 kJ/mol 1.369
1.377 2.106
2.154
1.179 1.209
1.218 1.216
2.207 2.494
1.376 1.381 2.225
2.243
1.170 1.208
1.232 1.229
Figure 10. Fulminic Acid/Acrolein (s-cis) Transition State Geometries
1(R)
1
2 3
2(R)
E(RHF)=130.48 kJ/mol E(B3LYP)=35.46 kJ/mol
E(RHF)=132.94 kJ/mol E(B3LYP)=49.18 kJ/mol 1.375
1.378 2.104
2.180
1.179 1.207
1.223 1.216
2.250 2.524
1.376 1.378 2.251
2.288
1.170 1.208
1.229 1.227
Figure 11. Fulminic Acid/Acrolein (s-trans) Transition State Geometries
1(R)
1
2 3
2(R)
E(RHF)= -209.54 kJ/mol E(B3LYP)= -169.19 kJ/mol
E(RHF)= -194.55 kJ/mol E(B3LYP)= -159.73 kJ/mol 1.367
1.374 2.118
2.169
1.178 1.209
1.222 1.216
2.237 2.506
1.374 1.378 2.193
2.238
1.172 1.208
1.233 1.229
