Supplementary Table I: Energies (in eV) of the lowest energy conformations of all species at PM3 solvent
molecules
amine ylide concerted
TG
amine radical
methyl radical
(CH3CN)n
0 -919.55246 -918.53052 -916.18989 -753.85556 -163.34787
1 -1364.45496 -1363.51022 -1361.09168 -1198.77851 -608.22562 -444.78432 2 -1809.35789 -1808.48006 -1806.00841 -1643.71649 -1053.11691 -889.65163 3 -2254.25388 -2253.44715 -2250.94727 -2088.61076 -1497.99804 -1334.53882 4 -2699.15002 -2698.38716 -2695.86987 -2533.46653 -1942.94176 -1779.42817 5 -3144.09455 -3143.32749 -3140.77760 -2978.33753 -2387.78415 -2224.29214
6 -3588.97328 -3588.26886 -3585.70203 -2269.24406
Supplementary Table II: Energies (in eV) of the lowest energy conformations of all species at
COSMO PM3 solvent molecules
amine ylide concerted
TG
amine radical
methyl radical
(CH3CN)n
0 -919.98747 -919.70171 -916.77013 -754.53010 -163.35848
1 -1365.23495 -1364.87056 -1362.03621 -1199.74740 -608.61534 -445.16197 2 -1810.57992 -1810.00205 -1807.35327 -1644.95582 -1053.86689 -890.42279 3 -2255.74902 -2255.33946 -2252.67862 -2090.07515 -1499.07328 -1335.58370 4 -2701.03144 -2700.62832 -2697.94264 -2535.07103 -1944.18155 -1780.74021
Supplementary Table IIIa. Optimised positions of acetonitrile molecules around amine
=1 =35.9 (COSMO)
R 1 1 2 2 R 1 1 2 2
1 6.05 69.9 43.6 137.4 136.1 5.50 69.0 181.9 146.6 21.6
2 5.30 81.1 29.1 116.0 186.2 5.77 48.7 164.7 151.9 268.9
4.69 129.5 38.5 17.7 120.4 5.96 83.0 44.4 139.9 125.0
3 5.58 52.0 180.8 152.0 271.0 5.73 62.4 164.5 135.7 217.2
5.34 84.1 33.9 126.1 168.3 5.33 94.0 41.7 106.9 195.1 4.75 128.6 51.9 11.8 112.0 4.67 133.2 133.1 134.6 96.6
4 5.55 54.1 164.5 129.5 332.6 5.70 64.4 173.6 145.4 335.2
5.12 81.6 29.0 110.6 184.6 5.82 84.6 51.0 121.3 177.3 4.05 125.0 159.1 111.9 12.7 5.02 88.4 234.3 75.5 92.3 4.78 133.1 38.4 28.4 132.4 4.69 134.2 132.1 136.6 57.1
5 5.81 52.1 128.0 94.2 132.3 6.64 34.7 127.1 122.3 190.8
4.88 83.2 185.7 122.7 87.1 5.63 66.1 183.4 147.7 325.8 5.57 88.4 37.4 116.1 169.6 4.94 84.4 247.4 81.8 136.7
4.67 133.7 52.4 1.6 122.7 5.75 84.5 51.1 119.3 188.8
4.71 140.8 135.2 137.9 269.7 4.74 129.5 123.5 140.6 18.1
6 6.34 29.1 160.5 106.5 227.8
Supplementary Table IIIb. Optimised positions of acetonitrile molecules around ylide
=1 =35.9 (COSMO)
R 1 1 2 2 R 1 1 2 2
1 3.97 111.8 165.4 57.17 188.2 5.47 127.9 123.9 113.0 198.8
2 5.19 98.6 155.6 87.6 205.5 4.67 62.9 75.5 105.2 190.0
4.20 145.3 115.2 19.54 227.4 5.37 120.1 125.7 94.8 197.6
3 4.53 97.4 117.5 73.5 146.5 6.54 23.9 129.0 115.1 187.0
5.20 98.2 159.0 95.8 200.5 4.55 71.5 6.5 100.7 162.1
4.21 146.1 124.7 16.6 234.0 6.38 116.3 187.8 69.7 238.8
4 4.89 54.2 36.0 105.9 178.2 6.83 1.49 130.0 129.7 125.5
5.35 99.6 219.4 133.0 182.5 5.23 52.3 302.3 88.0 204.0
3.99 109.2 35.9 9.3 209.5 5.05 64.6 16.0 118.3 179.0
4.02 110.5 162.0 59.8 199.8 4.78 111.6 218.3 109.9 320.0
5 5.88 27.2 22.4 137.3 140.1 6.91 1.77 167.8 136.4 112.4
4.87 64.6 320.8 48.5 185.5 4.92 54.9 200.4 96.8 210.5 5.02 101.9 158.8 93.4 146.5 5.03 68.0 17.9 122.7 175.9 5.41 102.2 218.0 136.6 167.3 5.24 114.3 214.1 120.9 188.8 4.21 144.1 111.6 16.3 229.5 7.37 130.6 331.6 80.5 123.9
6 5.82 38.7 239.7 101.0 75.3
Supplementary Table IIIc. Optimised positions of acetonitrile molecules around concerted TS
=1 =35.9 (COSMO)
R 1 1 2 2 R 1 1 2 2
1 5.04 59.3 330.8 118.2 154.2 5.31 54.8 333.2 127.2 147.6
2 5.42 96.7 192.6 125.7 150.5 6.20 34.8 267.3 154.7 198.5
4.02 111.3 129.3 62.6 223.1 5.44 55.0 348.4 124.0 193.1
3 5.34 53.9 14.1 117.9 172.9 6.97 17.0 197.1 139.4 194.7
5.73 55.7 302.4 132.9 172.5 6.31 48.7 283.1 147.8 194.2 4.68 102.3 19.9 7.4 179.6 5.36 58.9 355.1 122.9 174.8
4 6.79 22.4 205.7 132.9 181.0 6.96 17.9 197.5 137.6 192.4
5.94 47.4 294.9 146.5 189.7 5.71 45.7 5.2 143.8 77.7 5.24 61.9 7.7 120.1 178.3 6.29 48.2 283.7 148.1 195.9 4.68 110.1 15.9 0.9 69.5 4.99 122.7 306.6 114.6 102.7
5 6.65 20.9 215.8 130.5 185.1 6.94 19.0 197.5 135.7 191.3
5.86 50.0 301.0 147.9 193.0 5.73 44.3 6.9 143.2 76.4 5.04 67.3 12.3 118.8 173.5 6.28 47.9 284.2 147.6 194.7 4.47 113.6 45.5 8.83 356.4 5.68 98.3 221.1 132.1 134.2 4.40 117.7 109.5 121.4 193.4 5.07 118.6 307.3 116.9 91.5
6 5.72 31.2 224.8 103.7 188.1
Supplementary Table IIId. Optimised positions of acetonitrile molecules around amine radical
=1 =35.9 (COSMO)
R 1 1 2 2 R 1 1 2 2
1 5.25 76.3 0.7 111.6 167.5 4.70 65.6 172.0 89.1 194.9
2 5.03 73.8 25.4 106.1 141.3 4.33 72.6 167.4 85.5 192.3
4.43 115.5 62.8 20.5 139.9 5.35 82.8 3.0 116.3 162.3
3 5.21 64.0 165.0 105.4 200.2 5.70 43.8 235.1 86.4 165.2
5.46 73.6 0.2 118.4 172.9 5.32 59.7 167.7 104.6 174.6 4.46 111.1 142.2 10.1 231.4 4.41 140.5 49.2 122.8 67.5
4 6.43 40.9 5.1 81.7 173.1 5.92 47.5 233.8 84.1 160.2
4.59 72.7 183.1 92.4 178.3 5.27 61.2 168.8 103.7 181.3
4.64 99.4 17.6 103.9 144.5 4.63 71.6 2.8 76.1 168.8
4.40 132.3 72.0 16.9 92.6 4.47 137.8 49.1 125.3 88.0
5 6.62 31.5 94.8 106.9 217.8
Supplementary Table IIIe. Optimised positions of acetonitrile molecules around methyl radical
=1 =35.9 (COSMO)
R 1 1 2 2 R 1 1 2 2
1 4.68 12.6 83.5 131.5 166.9 4.71 109.4 185.5 133.4 11.2
2 4.64 109.7 179.7 129.8 357.1 4.66 115.0 347.8 131.2 299.2
4.06 161.9 345.1 111.9 197.5 4.50 139.5 161.9 124.0 221.5
3 3.96 41.8 161.6 108.5 172.4 4.05 45.9 150.8 118.4 158.5
4.45 97.1 5.0 122.3 6.4 4.57 58.4 41.7 140.1 287.0
4.49 133.3 166.7 124.4 188.8 4.54 139.0 159.3 126.7 232.8
4 3.92 47.1 146.2 109.0 162.7 4.06 44.4 150.5 115.8 164.3
4.52 78.8 67.2 68.1 12.8 4.88 55.2 40.8 151.7 287.9
4.49 133.3 166.7 124.4 188.8 4.49 111.0 356.4 125.8 281.9 3.84 122.5 119.9 106.6 262.7 3.69 119.5 121.0 103.2 294.4
5 6.62 31.5 94.8 106.9 217.8
