Supplementary Data:
The First Principle Computational Study for the Competitive Mechanisms of Oxidative Aromatization of 2-Substituted Imidazolines using KMnO4/SiO2
Avat (Arman) Taherpour1,2*, Ako Yari1, Fatemeh Ghasemhezaveh1 and Mohammad Ali Zolfigol3
1Department of Organic Chemistry, Faculty of Chemistry, Razi University, P.O.Box: 67149-67346, Kermanshah, Iran
2Medical Biology Research Center, Kermanshah University of Medical Sciences, Kermanshah, Iran
3Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran.
Table of Contents:
S-1: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the precursor a (4,5-dihydro-1H-imidazole).
S-2: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the precursor b (2-methyl-4,5-dihydro-1H-imidazole).
S-3: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the precursor c (2-phenyl-4,5-dihydro-1H-imidazole).
S-4: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the intermediate structure d (4,5-dihydro-1H-imidazol-4-ide).
S-5: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the intermediate structure e (2-methyl-4,5-dihydro-1H-imidazol-4-ide).
S-6: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the intermediate structure f (2-phenyl-4,5-dihydro-1H-imidazol-4-ide).
S-7: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the product g (1H-imidazole).
S-8: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the product h (2-methyl-1H-imidazole).
S-9: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the product i (2-phenyl-1H-imidazole).
S-10: Selected structural data for Concerted reaction. (Figure-1, compound; ).
S-11: Selected structural data for E1-cb reaction. (Figure-1, compound; ).
S-1: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the precursor a (4,5-dihydro-1H-imidazole).
a
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
MO: 1 2 3 4 5
Eigenvalues: -14.34830 -14.29966 -10.24182 -10.22081 -10.20603
(ev) -390.43739 -389.11370 -278.69410 -278.12259 -277.72029
S-2: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the precursor b (2-methyl-4,5-dihydro-1H-imidazole).
b
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -14.34114 -14.29179 -10.24266 -10.21598 -10.20117
(ev) -390.24246 -388.89956 -278.71720 -277.99119 -277.58799
S-3: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the precursor c (2-phenyl-4,5-dihydro-1H-imidazole).
c
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -14.34443 -14.29788 -10.24624 -10.21860 -10.20527
(ev) -390.33191 -389.06526 -278.81445 -278.06229 -277.69968
S-4: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the intermediate structure d (4,5-dihydro-1H-imidazol-4-ide).
d
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -15.34923 -15.34867 -11.05219 -11.02070 -10.98297
(ev) -417.67397 -417.65885 -300.74551 -299.88868 -298.86184
S-5: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the intermediate structure e (2-methyl-4,5-dihydro-1H-imidazol-4-ide).
e
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -15.36001 -15.34877 -11.05753 -11.04644 -11.02228
(ev) -417.96731 -417.66145 -300.89073 -300.58912 -299.93154
S-6: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the intermediate structure f (2-phenyl-4,5-dihydro-1H-imidazol-4-ide).
f
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -15.42155 -15.40256 -11.12157 -11.09752 -11.09671
(ev) -419.64196 -419.12514 -302.63351 -301.97897 -301.95705
S-7: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the product g (1H-imidazole).
g
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -14.39188 -14.30717 -10.23589 -10.21264 -10.19316
(ev) -391.62306 -389.31806 -278.53273 -277.90012 -277.36998
S-8: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the product h (2-methyl-1H-imidazole).
h
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -14.38338 -14.29933 -10.23727 -10.20682 -10.19141
(ev) -391.39196 -389.10481 -278.57027 -277.74191 -277.32251
S-9: Structure, Cartesian Coordinates and Closed-Shell Molecular Orbital Coefficients Eigenvalues of the product i (2-phenyl-1H-imidazole).
i
Point Group = C1 Order = 1 Nsymop = 1
Closed-Shell Molecular Orbital Coefficients
Eigenvalues: -14.39126 -14.30793 -10.24310 -10.21561 -10.20420
(ev) -391.60627 -389.33883 -278.72910 -277.98109 -277.67043
S-10: Selected structural data for the concerted reactions.
R = H / R = Me / R = Ph
Reactant / TS / Product / Reactant / TS / Product / Reactant / TS / Product
Bond length(Å)
C1-N1 / 1.400 / 1.367 / 1.372 / 1.400 / 1.367 / 1.372 / 1.400 / 1.367 / 1.372
C1-C4 / - / 1.477 / - / 1.498 / 1.477 / 1.498 / 1.531 / 1.531 / 1.531
C1-N2 / 1.283 / 1.311 / 1.319 / 1.283 / 1.311 / 1.319 / 1.283 / 1.311 / 1.319
N1-H1 / 1.012 / 1.007 / 1.008 / 1.012 / 1.007 / 1.008 / 1.012 / 1.007 / 1.008
N1-C2 / 1.470 / 1.412 / 1.382 / 1.470 / 1.412 / 1.382 / 1.470 / 1.412 / 1.382
N2-C3 / 1.474 / 1.411 / 1.379 / 1.474 / 1.411 / 1.379 / 1.474 / 1.411 / 1.379
C2-C3 / 1.553 / 1.464 / 1.370 / 1.553 / 1.464 / 1.370 / 1.553 / 1.464 / 1.370
C2-H2’ / 1.094 / 1.122 / - / 1.094 / 1.122 / - / 1.094 / 1.122 / -
C2-H2 / 1.100 / 1.808 / 1.079 / 1.100 / 1.808 / 1.079 / 1.100 / 1.808 / 1.079
C3-H3 / 1.098 / 1.128 / 1.081 / 1.098 / 1.128 / 1.081 / 1.098 / 1.128 / 1.081
C3-H3’ / 1.094 / 1.808 / - / 1.094 / 1.808 / - / 1.094 / 1.808 / -
Bond angle(º)
N1-C1-N2 / 110.83 / 110.83 / 110.84 / 116.41 / 118.08 / 110.84 / 116.41 / 110.83 / 110.84
N1-C1-C4 / - / - / 126.28 / 119.38 / 122.24 / 126.28 / 119.38 / 122.24 / 126.28
H1-N1-C1 / 127.03 / 127.03 / 105.78 / 117.24 / 109.00 / 105.78 / 117.24 / 127.03 / 105.78
C1-N2-C3 / 108.82 / 108.82 / 110.77 / 106.26 / 105.36 / 110.77 / 106.26 / 108.82 / 110.77
N2-C3-C2 / 105.44 / 105.44 / 104.91 / 105.93 / 109.55 / 104.91 / 105.93 / 105.44 / 104.91
C3-C2-N1 / 104.50 / 104.50 / 107.70 / 100.46 / 105.65 / 107.70 / 100.46 / 104.50 / 107.70
C2-N1-C1 / 108.41 / 108.41 / - / 106.17 / 100.08 / - / 106.17 / 108.41 / -
H2’-C2-C3 / 125.69 / 125.69 / 127.87 / 113.30 / 109.55 / 127.87 / 113.30 / 125.69 / 127.87
H3-C3-C2 / 121.76 / 121.76 / - / 111.02 / 126.41 / - / 111.02 / 121.76 / -
H2’-C2-H2 / 87.35 / 87.35 / - / 108.26 / 108.83 / - / 108.26 / 87.35 / -
H3-C3-H3’ / 87.01 / 87.01 / 132.84 / 107.26 / 95.77 / 132.84 / 107.26 / 87.01 / 132.84
H2-C2-C3 / 110.88 / 110.88 / - / 111.49 / 116.24 / - / 111.49 / 110.88 / -
H3’-C3-C2 / 109.98 / 109.98 / 110.84 / 112.82 / 100.40 / 110.84 / 112.82 / 109.98 / 110.84
Dihedral angle(º)
N1-C1-C4-C5 / - / - / - / - / - / - / -15.26 / -8.45 / -0.16
H1-N1-C1-C4 / - / - / - / -34.14 / -3.19 / - / -34.14 / -3.19 / 0.20
N1-C2-C3-N2 / 20.25 / 9.65 / 0.00 / 20.25 / 9.65 / 0.00 / 20.25 / 9.65 / 0.00
C2-C3-N2-C1 / -12.76 / -14.32 / 0.00 / -12.76 / -14.32 / 0.00 / -12.76 / -14.32 / 0.00
C3-N2-C1-N1 / -0.89 / 13.58 / 0.00 / -0.89 / 13.58 / 0.00 / -0.89 / 13.58 / 0.01
N2-C1-N1-C2 / 14.95 / -7.06 / 0.00 / 14.95 / -7.06 / 0.00 / 14.95 / -7.06 / -0.01
C1-N1-C2-C3 / -20.43 / -2.09 / 0.00 / -20.43 / -2.09 / 0.00 / -20.43 / -2.09 / 0.01
H2’-C2-C3-H3 / 21.40 / 7.08 / - / 21.40 / 7.08 / - / 21.40 / 7.08 / -
H2-C2-C3-H3’ / 23.39 / 3.97 / - / 23.39 / 3.97 / - / 23.39 / 3.97 / -
C2-N1-C1-C4 / - / - / -179.87 / -168.13 / 177.45 / -179.87 / -168.13 / 177.45 / -179.87
S-11: Selected structural data for the stepwise E1cb' and E1cb'Cat. reaction.
R = H / R = Me / R = Ph
React. / TS1 / [In.] / TS2 / TS3 / Prod. / React. / TS1 / [In.] / TS2 / TS3 / Prod. / React. / TS1 / [In.] / TS2 / TS3 / Prod.
Bond length(Å)
C1-N1 / 1.400 / 1.468 / 1.479 / 1.468 / 1.434 / 1.372 / 1.400 / 1.468 / 1.479 / 1.468 / 1.434 / 1.372 / 1.400 / 1.467 / 1.479 / 1.467 / 1.431 / 1.372
C1-C4 / - / - / - / - / - / - / 1.498 / 1.531 / 1.492 / 1.531 / 1.492 / 1.494 / 1.531 / 1.531 / 1.531 / 1.531 / 1.531 / 1.531
C1-N2 / 1.283 / 1.330 / 1.339 / 1.330 / 1.330 / 1.319 / 1.283 / 1.330 / 1.339 / 1.330 / 1.330 / 1.319 / 1.283 / 1.330 / 1.339 / 1.330 / 1.330 / 1.319
N1-H1 / 1.012 / 1.027 / 1.047 / 1.027 / 1.047 / 1.008 / 1.012 / 1.027 / 1.047 / 1.027 / 1.047 / 1.008 / 1.012 / 1.027 / 1.047 / 1.027 / 1.047 / 1.008
N1-C3 / 1.470 / 1.485 / 1.490 / 1.485 / 1.445 / 1.382 / 1.470 / 1.485 / 1.490 / 1.485 / 1.445 / 1.382 / 1.470 / 1.485 / 1.490 / 1.485 / 1.442 / 1.382
N2-C2 / 1.474 / 1.384 / 1.351 / 1.384 / 1.362 / 1.379 / 1.474 / 1.381 / 1.351 / 1.381 / 1.362 / 1.379 / 1.474 / 1.382 / 1.351 / 1.382 / 1.363 / 1.379
C2-C3 / 1.553 / 1.521 / 1.514 / 1.521 / 1.447 / 1.370 / 1.553 / 1.521 / 1.514 / 1.521 / 1.447 / 1.370 / 1.553 / 1.521 / 1.514 / 1.521 / 1.450 / 1.370
C2-H2’ / 1.094 / 1.118 / 1.121 / 1.118 / 1.501 / - / 1.094 / 1.118 / 1.121 / 1.118 / 1.501 / - / 1.094 / 1.118 / 1.121 / 1.118 / 1.520 / -
C2-H2 / 1.100 / 1.950 / 1.100 / 1.092 / - / 1.079 / 1.100 / 1.955 / 1.100 / 1.092 / - / 1.079 / 1.100 / 1.960 / 1.100 / 1.092 / - / 1.079
C3-H3 / 1.098 / 1.094 / 1.093 / 1.094 / 1.086 / 1.081 / 1.098 / 1.094 / 1.093 / 1.094 / 1.086 / 1.081 / 1.098 / 1.094 / 1.093 / 1.094 / 1.086 / 1.081
O2-H3’ / 1.094 / 1.092 / - / 1.961 / - / - / 1.094 / 1.092 / - / 1.982 / - / - / 1.094 / 1.092 / - / 1.992 / - / -
H3’-C3 / - / 1.275 / 0.971 / 2.096 / 1.399 / - / - / 1.267 / 0.971 / 2.100 / 1.399 / - / - / 1.290 / 0.971 / 2.108 / 1.420 / -
Bond angle(º)
N1-C1-N2 / 116.41 / 117.97 / 111.56 / 117.97 / 111.56 / 110.84 / 116.41 / 118.08 / 111.56 / 118.08 / 111.56 / 110.84 / 116.41 / 117.97 / 111.56 / 117.97 / 111.56 / 110.84
N1-C1-C4 / - / - / - / - / - / - / 119.38 / 121.50 / 116.78 / 121.50 / 116.78 / 123.30 / 119.38 / 121.57 / 116.78 / 121.57 / 116.78 / 123.30
H1-N1-C1 / 117.24 / 108.97 / 104.12 / 108.97 / 119.77 / 126.28 / 117.24 / 109.00 / 104.12 / 109.00 / 119.77 / 126.28 / 117.24 / 108.97 / 104.12 / 108.97 / 120.31 / 126.28
C1-N2-C3 / 106.26 / 105.55 / 109.13 / 105.55 / 111.47 / 105.78 / 106.26 / 105.36 / 109.13 / 105.36 / 111.47 / 105.78 / 106.26 / 105.56 / 109.13 / 105.56 / 111.47 / 105.78
N2-C3-C2 / 105.93 / 109.27 / 106.82 / 109.27 / 100.41 / 110.77 / 105.93 / 109.55 / 106.82 / 109.55 / 100.41 / 110.77 / 105.93 / 109.32 / 106.82 / 109.32 / 100.28 / 110.77
C3-C2-N1 / 100.46 / 105.80 / 102.10 / 105.80 / 111.17 / 104.91 / 100.46 / 105.65 / 102.10 / 105.65 / 111.17 / 104.91 / 100.46 / 105.74 / 102.10 / 105.74 / 111.11 / 104.91
C2-N1-C1 / 106.17 / 100.13 / 99.07 / 100.13 / 94.89 / 107.70 / 106.17 / 100.08 / 99.07 / 100.08 / 94.89 / 107.70 / 106.17 / 100.13 / 99.07 / 100.13 / 95.09 / 107.70
H2’-C2-C3 / 113.30 / 109.51 / 112.17 / 109.51 / 127.48 / - / 113.30 / 109.55 / 112.17 / 109.55 / 127.48 / - / 113.30 / 109.53 / 112.17 / 109.53 / 127.43 / -
H3-C3-C2 / 111.02 / 126.54 / 122.78 / 126.54 / 124.77 / 127.87 / 111.02 / 126.41 / 122.78 / 126.41 / 124.77 / 127.87 / 111.02 / 126.49 / 122.78 / 126.49 / 124.90 / 127.87
H2’-C2-H2 / 108.26 / 108.83 / 107.28 / 108.83 / 96.04 / - / 108.26 / 108.83 / 107.28 / 108.83 / 96.04 / - / 108.26 / 108.83 / 107.28 / 108.83 / 95.24 / -
H3-C3-H3’ / 107.26 / 95.77 / - / 95.77 / - / - / 107.26 / 95.77 / - / 95.77 / - / - / 107.26 / 95.77 / - / 95.77 / - / -
H2-C2-C3 / 111.49 / 116.14 / 117.59 / 116.14 / 113.00 / 132.84 / 111.49 / 116.24 / 117.59 / 116.24 / 113.00 / 132.84 / 111.49 / 116.18 / 117.59 / 116.18 / 113.48 / 132.84
H3’-C3-C2 / 112.82 / 100.44 / - / 100.44 / - / - / 112.82 / 100.40 / - / 100.40 / - / - / 112.82 / 100.43 / - / 100.43 / - / -
Dihedral angle(º)
N1-C1-C4-C5 / - / - / - / - / - / - / - / - / - / - / -15.26 / -6.93 / -4.50 / -6.93 / -2.15 / -0.16
H1-N1-C1-C4 / - / - / - / - / - / - / -34.14 / -61.88 / -67.17 / -61.88 / -26.11 / 0.20 / -34.14 / -61.86 / -67.17 / -61.86 / -23.41 / 0.20
N1-C2-C3-N2 / 20.25 / -10.83 / -29.65 / -10.83 / -24.30 / 0.00 / 20.25 / -10.83 / -29.65 / -10.83 / -24.30 / 0.00 / 20.25 / -10.83 / -29.65 / -10.83 / -24.22 / 0.00
C2-C3-N2-C1 / -12.76 / 11.34 / 13.55 / 11.34 / 4.55 / 0.00 / -12.76 / 11.33 / 13.55 / 11.33 / 4.55 / 0.00 / -12.76 / 11.34 / 13.55 / 11.34 / 4.50 / 0.00
C3-N2-C1-N1 / -0.89 / -8.21 / 8.59 / -8.21 / 16.63 / 0.00 / -0.89 / -8.19 / 8.59 / -8.19 / 16.63 / 0.01 / -0.89 / -8.21 / 8.59 / -8.21 / 16.63 / 0.01
N2-C1-N1-C2 / 14.95 / 1.33 / -26.53 / 1.33 / -28.59 / 0.00 / 14.95 / 1.33 / -26.53 / 1.33 / -28.59 / 0.00 / 14.95 / 1.33 / -26.53 / 1.33 / -28.63 / -0.01
C1-N1-C2-C3 / -20.43 / 5.53 / 31.65 / 5.53 / 31.69 / 0.00 / -20.43 / 5.51 / 31.65 / 5.51 / 31.69 / 0.00 / -20.43 / 5.52 / 31.56 / 5.52 / 31.68 / 0.01
H2’-C2-C3-H3 / 21.40 / -42.81 / -60.97 / -42.81 / -83.21 / - / 21.40 / -42.93 / -60.97 / -42.93 / -83.21 / - / 21.40 / -42.85 / -60.97 / -42.85 / -83.14 / -
H2-C2-C3-H3’ / 23.39 / -24.38 / 64.12 / -24.38 / 34.80 / - / 23.39 / -24.30 / 64.12 / -24.30 / 34.80 / - / 23.39 / -24.35 / 64.12 / -24.35 / 34.11 / -
C2-N1-C1-C4 / - / - / - / - / - / -179.87 / -168.13 / -178.13 / -172.98 / -178.13 / -175.04 / -179.87 / -168.13 / -178.13 / -172.98 / -178.13 / -175.09 / -179.87