Table 2. 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

TS F-C extrusion

n1

TS Fax-ax interconversion

n1

TS C-C extrusion

n1

4,a W=I, Z=F,

X=CN, Y=H

-7229.4933 (46.5)

-7234.1711 (28.9)

195.5 (62.3)

663 i

473 i

945 i

-7229.5042 (40.8)

-7234.1751 (25.4)

145.6 (12.4)

262 i

183 i

37 i

-7229.4755 (57.7)

-7234.1625 (34.4)

184.2 (51.0)

729 i

533 i

786 i

5,a W=I, Z=F,

X=H, Y=CN

-7229.5057 (35.0)

-7234.1796 (20.4)

186.8 (50.9)

553 i

398 i

835 i

-7229.5042 (36.0)

-7234.1751 (22.6)

145.6 (9.7)

262 i

183 i

37 i

-7229.4770 (53.0)

-7234.1624 (31.5)

182.2 (46.3)

725 i

520 i

762 i

6,b W=I, Z=F,

X=OCH3, Y=H

-7251.5289 (41.1)

-7256.3285 (24.4)

125.3 (59.4)

610 i

433 i

910 i

-7251.5371 (36.0)

-7256.3304 (22.5)

85.7 (19.8)

260 i

188 i

161 i

-7251.5050 (56.1)

-7256.3139 (33.9)

116.0 (50.1)

768 i

527 i

781 i

7,b W=I, Z=F,

X=H, Y=OCH3

-7251.5186 (48.2)

-7256.3203 (30.6)

122.3 (55.4)

652 i

459 i

862 i

-7251.5371 (36.6)

-7256.3304 (23.3)

85.7 (18.8)

260 i

188 i

161 i

-7251.5007 (59.4)

-7256.3092 (37.7)

116.5 (49.7)

731 i

557 i

772 i

8,c W=I, Z=F,

X=CN, Y=OCH3

-7342.7350 (52.7)

-7348.0589 (32.3)

151.6 (59.6)

682 i

481 i

877 i

-7342.7551 (40.1)

-7348.0700 (25.3)

113.1 (20.3)

260 i

199 i

162 i

-7342.7229 (60.3)

-7348.0545 (36.2)

141.7 (48.9)

722 i

544 i

735 i

9,c W=I, Z=F,

X=OCH3, Y=CN

-7342.7588 (32.6)

-7348.0770 (17.3)

145.0 (50.3)

531 i

371 i

822 i

-7342.7551 (35.0)

-7348.0700 (21.7)

113.1 (18.4)

259 i

199 i

162 i

-7342.7320 (49.4)

-7348.0617 (27.7)

138.1 (43.4)

719 i

497 i

698 i

a Energy of the ground state of 2 relative to 3 is &endash; 3.70, -2.86, -2.71 kcal mol-1; energy of the transition state of 2 relative to 3 is + 7.78, +5.33, +8.72 kcal mol-1. b Energy of the ground state of 4 relative to 5 is &endash;+0.63, +0.76, -1.02 kcal mol-1; energy of the transition state of 4 relative to 5 is &endash; 6.46, -5.15, +2.96 kcal mol-1. c Energy of the ground state of 6 relative to 7 is &endash; 5.15, -3.65, -2.71 kcal mol-1; energy of the transition state of 6 relative to 7 is + 14.93, +11.36, +6.66 kcal mol-1.