Table 3. Energies (activation barriers) and first normal mode (cm-1) for the stationary point structures (RHF/3-21G(d)/Hartree, B3LYP/3-21G(d)/Hartree, MNDOD/kcal mol-1).
|
Compound |
F-C extrusion |
n1, n2 |
Fax-ax interconversion |
n1, n2 |
|
10,a W=I, Z=F, X=SiH3, Y=H |
-7426.9402 (43.1) -7431.7065 (25.7) 157.9 (61.2) |
457 i 939 i |
-7426.9498 (37.1) -7431.7096 (23.8) 117.0 (20.3) |
190 i 156 i |
|
11,a W=I, Z=F, X=H, Y=SiH3 |
-7426.9456 (39.7) -7431.7102 (23.3) 151.8 (53.0) |
426 i 844 i |
-7426.9498 (37.0) -7431.7096 (23.7) 117.0 (18.2) |
190 i 156 i |
|
12,b W=I, Z=F, X=CN, Y=SiH3 |
-7518.1600 (43.7) -7523.4468 (25.8) 181.5 (55.9) |
448 i 866 i |
-7518.1662 (39.8) -7523.4478 (25.3) 145.4 (19.8) |
260 i, 20 i 198 i 154 i |
|
13,b W=I, Z=F, X=SiH3, Y=CN |
-7518.1677 (35.0) -7523.4522 (19.7) 178.9 (52.6) |
553 i, 7 i 399 i 849 i |
-7518.1662 (36.0) -7523.4478 (22.5) 145.4 (19.1) |
260 i, 20 i 198 i 154 i |
|
14,c W=Br, Z=F, X=CN, Y=OCH3
|
-3015.0612 (29.2) -3019.4325 (16.2) 166.8 (44.6) |
456 i 838 i |
-3015.0522 (34.8) -3019.4247 (21.1) 131.7 (9.5) |
198 i 121 i |
|
15,c W=Br, Z=F, X=OCH3, Y=CN |
-3015.0829 (11.0) -3019.4484 (2.4) 162.0 (37.0) |
253 i 770 i |
-3015.0522 (30.3) -3019.4247 (17.3) 131.7 (6.7) |
198 i 121 i |
|
16,d W=Cl, Z=F, X=CN, Y=OCH3 |
-912.1487 (14.2) -915.4553 (6.6) 166.4 (42.6) |
427 i 796 i |
-912.1222 (30.8) -915.4318 (21.4) 126.5 (2.7) |
227 i 95 i |
|
17,d W=Cl, Z=F, X=OCH3, Y=CN |
-912.1670 (0.9) e 158.9 (33.6) |
320 i
722 i |
-912.1222 (29.0) -915.4318 (e) 126.5 (1.1) |
227 i 95 i |
|
18,f W=I, Z=Cl, X=CN, Y=OCH3 |
-7701.2476 (51.4) -7706.8835 (34.4) 161.5 (42.8) |
448 i 588 i |
-7701.2901 (24.7) -7706.9085 (18.7) 131.2 (12.4) |
113 i 114 i 78 i |
|
19,f W=I, Z=Cl, X=OCH3, Y=CN |
-7701.2739 (30.5) -7706.9041 (17.9) 153.9 (33.1) |
429 i 287 i 397, 69 i |
-7701.2901 (20.3) -7706.9085 (15.1) 131.2 (0.4) |
113 i 114 i 78 i |
|
20,g W=I, Z=CN, X=CN, Y=OCH3 |
-7335.5804 (57.5) -7341.0478 (37.0) 229.1 (48.8) |
625 i 879 i |
-7335.6036 (42.9) -7341.0505 (35.4) 206.6 (26.3) |
222 i 240 i 201, 62 i |
|
21,g W=I, Z=CN, X=OCH3, Y=CN |
-7335.6009 (38.6) -7341.0602 (23.9) 224.1 (40.5) |
719 i 546 i 835 i |
-7335.6036 (37.0) -7341.0505 (30.0) 206.6 (23.0) |
222 i 240 i 201, 62 i |
a Energy of the ground state of 10 relative to 11 is &endash;0.06, -0.11, -2.09 kcal mol-1; energy of the transition state of 10 relative to 11 is +3.39, +2.32, +6.16 kcal mol-1. b Energy of the ground state of 12 relative to 13 is &endash;3.89, -2.74, -0.71 kcal mol-1; energy of the transition state of 12 relative to 13 is +4.83, +3.39, +2.58 kcal mol-1. c Energy of the ground state of 14 relative to 15 is &endash;4.58, -3.85, -2.81 kcal mol-1; energy of the transition state of 14 relative to 15 is +13.61, +9.98, +4.77 kcal mol-1. d Energy of the ground state of 16 relative to 17 is &endash;1.82, e, -1.60 kcal mol-1; energy of the transition state of 16 relative to 17 is +11.48, e, +7.42 kcal mol-1. e Ground state structure converges to the products on optimisation. f Energy of the ground state of 18 relative to 19 is &endash;4.39, -3.58, -2.02 kcal mol-1; energy of the transition state of 18 relative to 19 is +16.50, +12.93, +7.59 kcal mol-1. g Energy of the ground state of 20 relative to 21 is &endash;5.95, -5.35, -3.32 kcal mol-1; energy of the transition state of 20 relative to 21 is +12.86, +7.78, +4.99 kcal mol-1.