Table 5. Energies (activation barriers) and first normal mode (cm-1) for the stationary point structures (RHF/3-21G(d)/Hartree, B3LYP/3-21G(d)/Hartree, B3LYP/DZVP/Hartree, MNDOD/Kcal mol-1).
|
Compound |
GS |
F-C extrusion |
n1 |
Fax-ax interconversiona |
n1 |
|
22, X1=Y1=H, X2=Y2=H |
-14276.7220 (18.2)b -14284.9882 (24.3) -14346.2180 (13.9) 192.8 (21.2) |
-14276.6557 (41.6)c -14284.9473 (25.7) -14346.1794 (24.2) 247.7 (54.8) |
583 i 418 i 413 i 794 i |
-14276.7010 (13.2)d -14284.9837 (2.8) -14346.2132 (3.0) 0.0 |
223 i 99 i 115 i
|
|
23, X1=CN, Y1=OCH3, X2=CN, Y2=OCH3 |
-14685.6669 (18.1) -14696.2596 (24.4) 163.4 (22.4) |
-14685.5851 (51.3) -14696.2081 (32.3) 217.2 (53.8) |
633 i 454 i 809 i |
-14685.6377 (18.3) - 0.0 |
216 i
|
|
24, X1=CN, Y1=OCH3, X2=OCH3, Y2=CN |
-14685.6597 (18.7) -14696.2547 (25.0) 164.3 (23.3) |
-14685.6088 (31.9) -14696.2255 (18.3) 212.7 (48.4) |
486 i
740 i |
-14685.6381 (13.6) - 0.0 |
214 i
|
|
25, X1=OCH3, Y1=CN, X2=OCH3, Y2=CN |
-14685.6529 (19.7)
163.4 (26.0) |
-14685.6028 (31.5) 211.8 (48.4) |
481 i 328 i 744 i |
-14685.6377 (9.6) - 0.0 |
216 i
|
|
26, X1=OCH3, Y1=CN, X2=CN, Y2=OCH3 |
-14685.6597 (18.7) - 164.3 (23.3) |
-14685.5791 (50.6) 216.1 (51.8) |
621 i
812 i |
-14685.6381 (13.6) - 0.0 |
214 i
|
a MNDO-d predicts a symmetrical dimer. b Corresponding values for Z=Cl; -14993.7433 (16.1) Z=Br; -19199.4820 (17.1). c Corresponding values for Z=Cl, -14993.6685 (46.9). dCorresponding value for Z=Cl; 0.0.