suppmat1565.doc 305KB Jun 05 2011 09:30:52 PM

(1)

Supplementary Material for:

B3LYP Calculations on Homaromaticity in

Substituted Semibullvalenes and Barbaralanes

DAVID A. HROVAT,1 RICHARD VAUGHAN WILLIAMS,2 ALAN C. GOREN, 3 WESTON THATCHER BORDEN1

1

Department of Chemistry, Box 351700, University of Washington, Seattle, WA 981951700

2

Department of Chemistry, Box 442343, University of Idaho, Moscow, ID 838442343

3

Department of Chemistry, Transylvania University, Lexington, KY 40508

RHF and RB3LYP/631G* optimized geometries, energies, and thermal corrections for the structures discussed in the text. (31 pages).

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11

X Y Z C1 0.637522 0.294381

1.103855

C2 1.433353 0.143534 0.103490

C3 0.789971 1.359434 0.647914

C4 0.353494 1.623558 0.005564

C5 0.691766 0.500401 0.980979

C6 1.550944 0.420651 0.094511

C7 0.775045 1.349123 0.517041

C8 0.597252 1.281264 0.016651

H9 1.105034 0.496070 2.062824

C10 2.856180 0.033843 0.182775

H11 1.195958 1.913029 1.486803

H12 1.056138 2.412889 0.239784

H13 1.160115 0.803938 1.919496

C14 2.925284 0.168471 0.169327

H15 1.107458 2.027652 1.294520

H16 1.255373 2.142483 0.053127

N17 4.006663 0.188309 0.254926

N18 4.055110 0.054195 0.344266

(12) 1.511 (15) 1.554 (18) 1.494 (19) 1.086 (23) 1.479 (28) 1.654 (210) 1.436 (34) 1.343 (311) 1.084 (45) 1.526 (412) 1.085 (56) 1.540 (513) 1.092 (67) 1.356 (614) 1.422 (78) 1.462 (715) 1.084 (816) 1.085 (1017) 1.163 (1418) 1.165 (215) 103.8 (218) 66.8 (219) 122.2 (518) 104.8 (519) 122.2 (819) 123.5 (123) 107.7 (128) 56.1 (1210) 122.0 (328) 120.5 (3210) 120.8 (8210) 113.4 (234) 110.7 (2311) 122.8 (4311) 126.5 (345) 110.8 (3412) 125.8 (5412) 122.5 (154) 103.7 (156) 102.5 (1513) 116.2 (456) 101.3 (4513) 116.1 (6513) 114.9 (567) 110.5 (5614) 122.7 (7614) 126.2 (678) 110.5 (6715) 125.2 (8715) 124.2 (182) 57.1 (187) 108.2 (1816) 122.2 (287) 119.8 (2816) 112.1 (7816) 121.4 (21017) 179.3 (61418) 177.8

(3)

(8123) 115.3 (81210) 98.3 (9123) 128.6 (9128) 116.1 (91210) 17.8 (2154) 17.8 (2156) 87.3 (21513) 146.5 (8154) 87.1 (8156) 18.1 (81513) 144.2 (9154) 125.7 (9156) 129.2 (91513) 3.0 (2187) 114.2 (21816) 96.9 (5182) 99.0 (5187) 15.2 (51816) 164.1 (9182) 114.3 (9187) 131.5 (91816) 17.4 (1234) 5.8 (12311) 176.4 (8234) 54.7 (82311) 123.0 (10234) 152.7 (102311) 29.6 (1287) 93.4 (12816) 115.1 (3281) 91.6 (3287) 1.8 (32816) 153.3 (10281) 113.9 (10287) 152.7 (102816) 1.2 (121017) 101.4 (321017) 116.5 (821017) 37.9 (2345) 6.5 (23412) 175.3 (11345) 171.2 (113412) 2.4 (3451) 15.6 (3456) 90.5 (34513) 144.3 (12451) 175.2 (12456) 78.7 (124513) 46.5 (1567) 15.7 (15614) 172.8 (4567) 91.3 (45614) 80.2 (13567) 142.7 (135614) 45.8 (5678) 6.8 (56715) 171.2 (14678) 177.9 (146715) 0.1 (561418) 35.0 (761418) 154.9 (6781) 5.6 (6782) 56.3 (67816) 154.8 (15781) 176.4 (15782) 121.7 (157816) 27.1

Frequencies(cm1):

81.1 107.1 162.3 178.9 295.4 320.8 388.6 439.7 482.2 534.0 555.8 567.4 575.9 601.6 666.5 734.3 783.6 815.0 829.9 868.5 887.8 911.8 940.4 954.7 976.7 989.0 1079.6 1087.7 1121.5 1172.7 1199.6 1242.6 1270.8 1281.1 1286.6 1344.6 1372.3 1404.0 1631.6 1648.7 2337.0 2351.8 3127.0 3201.9 3219.3 3225.8 3240.5 3247.2

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15

X Y Z C1 0.378731 0.685630

1.033734

C2 0.414472 1.523670 0.051981

C3 1.453009 0.768752 0.510829

C4 1.510035 0.484463 0.068226

C5 0.378731 0.685630 1.033734

C6 0.414472 1.523670 0.051981

C7 1.453009 0.768752 0.510829

C8 1.510035 0.484463 0.068226

H9 0.601789 1.134262 2.003748

C10 0.121164 2.879815 0.228371

H11 2.093975 1.119914 1.311415

H12 2.224196 1.263006 0.170063

H13 0.601789 1.134262 2.003748

C14 0.121164 2.879815 0.228371

H15 2.093975 1.119914 1.311415

H16 2.224196 1.263006 0.170063

N17 0.121164 4.003068 0.430102

N18 0.121164 4.003068 0.430102

(12) 1.515 (15) 1.567 (18) 1.501 (19) 1.092 (23) 1.402 (210) 1.416 (34) 1.382 (311) 1.084 (412) 1.083 (1017) 1.167 (2,8) 2.187

(215) 103.4 (218) 93.0 (219) 117.1 (518) 104.3 (519) 117.3 (819) 118.2 (123) 110.5 (1210) 123.4 (3210) 126.2 (234) 110.5 (2311) 124.1 (4311) 125.4 (345) 111.1 (3412) 125.9 (5412) 122.8 (21017) 178.5 (5123) 2.5 (51210) 177.3 (8123) 103.0

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(113412) 2.7

(bond)(plane) angle (113)(234) 1.5

Frequencies(cm1_):

_{77.3 102.2 158.1 174.4 218.8 244.5 285.6 435.0}

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11

X Y Z C1 0.664905 0.331115

1.076340

C2 1.484599 0.302175 0.013937

C3 0.778085 1.418476 0.568933

C4 0.424347 1.576102 0.048212

C5 0.691575 0.442368 1.014030

C6 1.538505 0.423005 0.082856

C7 0.768796 1.406508 0.497991

C8 0.533753 1.401519 0.049334

H9 1.118873 0.536400 2.045529

C10 2.863392 0.028352 0.218084

H11 1.152589 2.012342 1.394723

H12 1.177319 2.312945 0.206909

H13 1.150416 0.703349 1.969813

C14 2.895682 0.136282 0.213124

H15 1.102968 2.061948 1.294057

H16 1.284266 2.163919 0.114103

N17 3.994992 0.201827 0.376170

N18 4.017848 0.104594 0.417796

(12) 1.504 (15) 1.563 (18) 1.489 (19) 1.090 (23) 1.433 (28) 1.952 (210) 1.420 (34) 1.361 (311) 1.084 (45) 1.513 (412) 1.084 (56) 1.527 (513) 1.092 (67) 1.377 (614) 1.418 (78) 1.413 (715) 1.084 (816) 1.082 (1017) 1.166 (1418) 1.166 (4,6) 2.289

(7)

(5123) 5.8 (5128) 103.0 (51210) 171.8 (8123) 108.8 (81210) 85.1 (9123) 130.3 (9128) 120.9 (91210) 35.7 (2154) 8.7 (2156) 92.8 (21513) 139.2 (8154) 93.2 (8156) 8.3 (81513) 136.3 (9154) 127.6 (9156) 130.9 (91513) 2.8 (2187) 107.3 (21816) 82.4 (5182) 102.0 (5187) 5.4 (51816) 175.6 (9182) 119.7 (9187) 133.0 (91816) 37.3 (1234) 0.2 (12311) 177.7 (8234) 53.0 (82311) 124.5 (10234) 165.9 (102311) 16.5 (1287) 95.5 (12816) 120.6 (3281) 93.7 (3287) 1.9 (32816) 145.7 (10281) 119.1 (10287) 145.3 (102816) 1.5 (121017) 9.2 (321017) 154.7 (821017) 61.4 (2345) 6.0 (23412) 176.9 (11345) 171.5 (113412) 0.5 (3451) 9.3 (3456) 96.2 (34513) 139.6 (12451) 179.4 (12456) 75.1 (124513) 49.1 (1567) 9.0 (15614) 176.6 (4567) 97.4 (45614) 76.9 (13567) 137.5 (135614) 48.1 (5678) 6.1 (56715) 171.4 (14678) 179.8 (146715) 2.8 (561418) 47.4 (761418) 139.1 (6781) 0.3 (6782) 54.3 (67816) 169.8 (15781) 177.2 (15782) 123.1 (157816) 12.8

_{227.5 82.0 107.8 161.1 181.1 291.5 294.0 437.6}

481.8 489.4 557.7 561.8 572.3 586.6 628.3 736.3 786.2 811.6 825.6 866.4 885.1 904.8 934.5 945.4 991.5 998.1 1103.3 1118.5 1174.2 1196.8 1229.2 1255.3 1276.7 1290.9 1294.0 1343.6 1422.2 1440.1 1550.9 1591.1 2325.8 2329.0 3122.6 3149.5 3233.6 3239.1 3252.3 3261.5

(8)

11

X Y Z C1 0.631605 0.289303

1.090870

C2 1.410152 0.095247 0.127413

C3 0.801366 1.346946 0.662145

C4 0.309143 1.639237 0.007210

C5 0.680323 0.517303 0.956624

C6 1.543040 0.413143 0.097293

C7 0.797296 1.321983 0.519456

C8 0.600732 1.253023 0.037091

H9 1.091674 0.489418 2.040537

C10 2.849787 0.063836 0.173429

H11 1.224339 1.894203 1.482322

H12 0.969239 2.458019 0.224107

H13 1.137936 0.829064 1.884980

C14 2.936410 0.168548 0.149814

H15 1.139322 2.008934 1.269438

H16 1.211136 2.136921 0.041121

N17 3.977058 0.197165 0.213982

N18 4.040662 0.042965 0.317146

(12) 1.496 (15) 1.546 (18) 1.484 (19) 1.074 (23) 1.491 (28) 1.575 (210) 1.449 (34) 1.322 (311) 1.073 (45) 1.525 (412) 1.074 (56) 1.532 (513) 1.081 (67) 1.328 (614) 1.436 (78) 1.481 (715) 1.073 (816) 1.074 (1017) 1.136 (1418) 1.137 (215) 103.7 (218) 63.8 (219) 123.0 (518) 104.8 (519) 122.5 (819) 124.1 (123) 107.2 (128) 57.7 (1210) 121.0 (328) 122.0 (3210) 119.1 (8210) 114.7 (234) 110.5 (2311) 122.8 (4311) 126.7 (345) 110.8 (3412) 125.8 (5412) 122.6 (154) 103.4 (156) 102.1 (1513) 115.8 (456) 103.3 (4513) 115.7 (6513) 114.7 (567) 111.1 (5614) 122.6 (7614) 125.6 (678) 110.3 (6715) 125.7 (8715) 124.0 (182) 58.5 (187) 107.3 (1816) 121.7 (287) 120.4 (2816) 114.3 (7816) 119.8 (21017) 179.5 (61418) 178.3

(9)

(9128) 115.1 (91210) 13.7 (2154) 20.5 (2156) 86.5 (21513) 148.1 (8154) 86.5 (8156) 20.5 (81513) 145.8 (9154) 124.7 (9156) 128.3 (91513) 2.9 (2187) 115.5 (21816) 100.9 (5182) 98.2 (5187) 17.3 (51816) 160.9 (9182) 113.6 (9187) 130.8 (91816) 12.7 (1234) 7.3 (12311) 174.0 (8234) 54.9 (82311) 123.8 (10234) 149.3 (102311) 32.0 (1287) 92.5 (12816) 113.5 (3281) 91.0 (3287) 1.5 (32816) 155.5 (10281) 112.3 (10287) 155.2 (102816) 1.2 (121017) 95.9 (321017) 127.4 (821017) 30.0 (2345) 6.7 (23412) 176.6 (11345) 171.9 (113412) 2.0 (3451) 17.4 (3456) 88.7 (34513) 145.1 (12451) 172.3 (12456) 81.6 (124513) 44.6 (1567) 17.7 (15614) 171.4 (4567) 89.4 (45614) 81.5 (13567) 143.8 (135614) 45.3 (5678) 7.5 (56715) 171.9 (14678) 178.0 (146715) 1.4 (561418) 24.3 (761418) 166.1 (6781) 6.6 (6782) 56.5 (67816) 151.0 (15781) 174.0 (15782) 122.9 (157816) 29.6

_{88.8 117.2 179.1 197.6 318.0 351.7 464.3 490.6}

530.6 589.9 601.6 622.9 653.6 703.1 784.6 789.0 857.3 881.6 929.8 942.7 985.4 1011.9 1023.1 1043.3 1079.5 1092.1 1157.1 1188.5 1216.6 1246.0 1294.2 1348.3 1389.7 1410.7 1414.2 1464.8 1490.7 1537.1 1815.7 1825.8 2603.1 2609.7 3297.0 3377.1 3386.0 3398.0 3416.6 3423.0

(10)

15

X Y Z C1 0.370395 0.682626

1.059652

C2 0.390672 1.481372 0.044770

C3 1.415625 0.736442 0.514999

C4 1.470930 0.506806 0.069009

C5 0.370395 0.682626 1.059652

C6 0.390672 1.481372 0.044770

C7 1.415625 0.736442 0.514999

C8 1.470930 0.506806 0.069009

H9 0.589691 1.144042 2.010774

C10 0.111765 2.855722 0.236993

H11 2.032601 1.067894 1.327355

H12 2.187474 1.273044 0.148843

H13 0.589691 1.144042 2.010774

C14 0.111765 2.855722 0.236993

H15 2.032601 1.067894 1.327355

H16 2.187474 1.273044 0.148843

N17 0.111765 3.953285 0.437601

N18 0.111765 3.953285 0.437601

(12) 1.499 (15) 1.553 (18) 1.491 (19) 1.080 (23) 1.385 (210) 1.430 (34) 1.375 (311) 1.073 (412) 1.071 (1017) 1.138 (2,8) 2.101

(215) 103.1 (218) 89.3 (219) 118.2 (518) 104.4 (519) 118.2 (819) 119.1 (123) 111.3 (1210) 123.1 (3210) 125.5 (234) 110.1 (2311) 124.4 (4311) 125.3 (345) 111.0 (3412) 126.0 (5412) 123.0 (21017) 178.8 (5123) 1.0 (51210) 176.0 (8123) 103.6

(11)

(113412) 5.7

(bond)(plane) angle (113)(234) 2.8

_{489.8 90.1 121.2 177.9 199.1 294.5 329.0 470.5}

528.6 547.8 600.0 617.6 619.5 642.3 675.9 794.7 854.7 882.3 882.7 928.6 951.3 972.3 1036.7 1054.4 1070.4 1086.6 1186.4 1205.5 1266.3 1305.0 1351.4 1362.6 1398.1 1409.5 1427.5 1451.6 1546.3 1599.0 1612.7 1702.5 2583.4 2588.9 3300.4 3310.8 3414.4 3415.5 3439.6 3440.5

(12)

15

X Y Z C1 0.674674 0.649269

0.389391

C2 1.428679 0.488525 0.274287

C3 0.714001 0.863190 1.508334

C4 0.447626 0.195243 1.600324

C5 0.721732 0.632125 0.346763

C6 1.509407 0.404406 0.484809

C7 0.681115 1.128321 1.277431

C8 0.677978 0.608573 1.200190

C9 1.334371 1.932997 0.830134

C10 2.857593 0.602127 0.189574

H11 1.084517 1.611900 2.199486

H12 1.199412 0.334065 2.371173

C13 1.415286 1.972187 0.565552

C14 2.894882 0.650994 0.277498

H15 0.971940 1.997045 1.857643

H16 1.391961 0.769436 2.001799

N17 4.014437 0.693399 0.106726

N18 4.034949 0.804184 0.092808

H19 1.490768 2.611182 0.015806

H20 0.723983 2.451555 1.577582

H21 2.312508 1.726029 1.276148

H22 0.814228 2.621336 1.210481

H23 1.591335 2.490741 0.382687

H24 2.386717 1.823492 1.049200

(13)

(921) 1.095 (1017) 1.163 (1322) 1.095 (1323) 1.095 (1324) 1.095 (1418) 1.165

(215) 103.1 (218) 66.8 (219) 123.2 (518) 104.2 (519) 122.1 (819) 123.8 (123) 108.4 (128) 56.0 (1210) 121.9 (328) 120.4 (3210) 120.8 (8210) 113.1 (234) 110.5 (2311) 122.9 (4311) 126.5 (345) 111.6 (3412) 125.7 (5412) 121.9 (154) 103.3 (156) 102.0 (1513) 117.4 (456) 99.8 (4513) 116.1 (6513) 115.8 (567) 111.2 (5614) 122.3 (7614) 126.0 (678) 110.4 (6715) 125.2 (8715) 124.4 (182) 57.2 (187) 109.1 (1816) 121.7 (287) 119.7 (2816) 111.7 (7816) 121.4 (1919) 111.3 (1920) 111.0 (1921) 110.4 (19920) 108.3 (19921) 107.7 (20921) 108.0 (21017) 179.3 (51322) 110.9 (51323) 111.4 (51324) 110.3 (221323) 108.5 (221324) 107.9 (231324) 107.7 (61418) 177.5

(5123) 14.7 (5128) 100.0 (51210) 162.1 (8123) 114.8 (81210) 97.9 (9123) 129.0 (9128) 116.2 (91210) 18.3 (2154) 16.9 (2156) 86.3 (21513) 146.1 (8154) 85.9 (8156) 17.3 (81513) 144.9 (9154) 127.4 (9156) 129.4 (91513) 1.8 (2187) 113.6 (21816) 96.8 (5182) 98.4 (5187) 15.2 (51816) 164.8 (9182) 115.5 (9187) 130.9 (91816) 18.7 (21919) 79.4 (21920) 160.0 (21921) 40.2 (51919) 57.8 (51920) 62.9 (51921) 177.4 (81919) 162.0 (81920) 77.4 (81921) 42.4 (1234) 6.5 (12311) 176.0 (8234) 54.3 (82311) 123.2 (10234) 154.2 (102311) 28.3 (1287) 94.6 (12816) 114.7 (3281) 92.6 (3287) 2.0 (32816) 152.7 (10281) 113.9 (10287) 151.5 (102816) 0.8 (121017) 53.7 (321017) 163.0 (821017) 9.5 (2345) 5.4 (23412) 175.4 (11345) 171.9 (113412) 2.0 (3451) 14.4 (3456) 90.5 (34513) 144.3 (12451) 175.2 (12456) 79.9 (124513) 45.3 (1567) 14.7 (15614) 173.0 (4567) 91.2 (45614) 81.1 (13567) 143.4 (135614) 44.4 (151322) 62.7 (151323) 58.3 (151324) 177.9 (451322) 60.2 (451323) 178.9 (451324) 59.3 (651322) 176.7 (651323) 62.3 (651324) 57.2 (5678) 5.9 (56715) 171.8 (14678) 177.8 (146715) 0.2 (561418) 30.2 (761418) 158.7 (6781) 6.4 (6782) 56.1 (67816) 156.1 (15781) 176.0 (15782) 121.6 (157816) 26.3

Frequencies(cm1_):_{77.1 106.4 135.3 141.6 182.3 219.4 235.9 256.7}

(14)

11

X Y Z C1 0.571665 0.553621

0.630072

C2 1.568426 0.004569 0.377120

C3 1.113037 1.194656 0.939082

C4 0.081634 1.573284 0.359218

C5 0.571665 0.553621 0.630072

C6 1.568426 0.004569 0.377120

C7 1.113037 1.194656 0.939082

C8 0.081634 1.573284 0.359218

C9 1.113037 1.048845 1.962853

C10 2.802276 0.639791 0.664958

H11 1.616241 1.719491 1.743359

H12 0.645313 2.468569 0.594970

C13 1.113037 1.048845 1.962853

C14 2.802276 0.639791 0.664958

H15 1.616241 1.719491 1.743359

H16 0.645313 2.468569 0.594970

N17 3.821527 1.169847 0.868046

N18 3.821527 1.169847 0.868046

H19 1.528195 0.225499 2.553405

H20 0.326240 1.536449 2.547717

H21 1.913085 1.778482 1.798249

H22 0.326240 1.536449 2.547717

H23 1.528195 0.225499 2.553405

H24 1.913085 1.778482 1.798249

(15)

(215) 102.7 (218) 91.3 (219) 117.7 (518) 103.8 (519) 118.8 (819) 118.2 (123) 111.2 (1210) 122.9 (3210) 125.8 (234) 110.3 (2311) 124.1 (4311) 125.5 (345) 111.9 (3412) 125.8 (5412) 122.3 (1919) 111.3 (1920) 110.9 (1921) 110.2 (19920) 108.6 (19921) 107.8 (20921) 108.0 (21017) 178.3

(5123) 1.9 (51210) 177.0 (8123) 102.6 (81210) 78.6 (9123) 134.4 (91210) 44.5 (2154) 0.1 (2156) 94.4 (21513) 133.7 (8154) 94.7 (81513) 131.8 (91513) 1.8 (2187) 101.3 (21816) 76.4 (5187) 2.1 (51816) 179.8 (9187) 136.1 (91816) 46.3 (21919) 66.3 (21920) 172.7 (21921) 53.1 (51919) 58.6 (51920) 62.4 (51921) 178.0 (81919) 174.4 (81920) 64.6 (81921) 54.9 (1234) 3.3 (12311) 174.4 (10234) 175.5 (102311) 6.8 (121017) 40.0 (321017) 138.7 (2345) 3.4 (23412) 179.0 (11345) 174.2 (113412) 3.4

(bond)(plane) angle (113)(234) 1.9

_{74.8 100.6 136.7 138.0 191.8 192.9 227.5 241.4}

246.5 261.2 288.8 338.4 360.3 437.6 487.1 493.2 502.0 567.5 589.1 615.3 630.7 631.7 674.7 725.8 799.1 802.9 837.5 844.3 924.7 937.5 950.5 951.9 1069.6 1071.8 1109.1 1131.8 1144.3 1191.1 1196.2 1238.8 1263.8 1273.7 1300.8 1357.9 1435.7 1445.6 1469.9 1483.2 1488.2 1515.1 1517.1 1529.2 1530.9 1554.2 2316.0 2316.5 3056.0 3060.1 3127.1 3128.8 3129.8 3135.0 3230.8 3231.6 3248.7 3249.3

(16)

15

X Y Z C1 0.700320 0.641519

0.366827

C2 1.465672 0.405908 0.406657

C3 0.694869 0.878933 1.512377

C4 0.518420 0.261994 1.541398

C5 0.721633 0.636937 0.340337

C6 1.499736 0.386825 0.490675

C7 0.677084 1.033126 1.387764

C8 0.617073 0.477765 1.351110

C9 1.362952 1.954132 0.738270

C10 2.855924 0.642302 0.227734

H11 1.031129 1.656063 2.189391

H12 1.315406 0.462549 2.249369

C13 1.404414 1.976028 0.586076

C14 2.870537 0.673495 0.260395

H15 0.972346 1.880371 1.996427

H16 1.412882 0.702172 2.051026

N17 3.997320 0.819311 0.070252

N18 4.003800 0.865694 0.064428

H19 1.503862 2.589701 0.142239

H20 2.348273 1.770568 1.179282

H21 0.760856 2.502515 1.470261

H22 0.810766 2.599063 1.262975

H23 1.556235 2.523625 0.349945

H24 2.386817 1.821106 1.044965

(17)

(921) 1.095 (1017) 1.166 (1322) 1.095 (1323) 1.095 (1324) 1.095 (1418) 1.166

(215) 102.9 (218) 81.1 (219) 120.3 (518) 104.0 (519) 120.2 (819) 120.8 (123) 110.6 (128) 49.0 (1210) 123.1 (328) 116.7 (3210) 124.8 (8210) 107.8 (234) 110.3 (2311) 123.6 (4311) 126.0 (345) 111.8 (3412) 125.8 (5412) 121.9 (154) 103.6 (156) 102.4 (1513) 118.1 (456) 95.8 (4513) 117.0 (6513) 116.6 (567) 111.3 (5614) 122.5 (7614) 126.0 (678) 110.3 (6715) 124.7 (8715) 124.9 (182) 49.8 (187) 111.3 (1816) 122.7 (287) 115.9 (2816) 105.7 (7816) 125.2 (1919) 111.2 (1920) 110.3 (1921) 110.9 (19920) 107.8 (19921) 108.5 (20921) 108.0 (21017) 179.0 (51322) 110.9 (51323) 111.3 (51324) 110.2 (221323) 108.6 (221324) 107.9 (231324) 107.7 (61418) 177.8

(5123) 5.6 (5128) 102.4 (51210) 172.4 (8123) 108.0 (81210) 85.2 (9123) 131.4 (9128) 120.6 (91210) 35.4 (2154) 7.8 (2156) 91.4 (21513) 139.0 (8154) 91.7 (8156) 7.5 (81513) 137.1 (9154) 129.2 (9156) 131.5 (91513) 1.9 (2187) 106.5 (21816) 83.0 (5182) 101.2 (5187) 5.3 (51816) 175.8 (9182) 120.1 (9187) 133.4 (91816) 37.1 (21919) 71.4 (21920) 48.1 (21921) 167.7 (51919) 58.3 (51920) 177.9 (51921) 62.5 (81919) 169.5 (81920) 49.9 (81921) 69.7 (1234) 0.8 (12311) 178.0 (8234) 52.7 (82311) 124.5 (10234) 167.3 (102311) 15.5 (1287) 96.9 (12816) 119.9 (3281) 94.9 (3287) 1.9 (32816) 145.2 (10281) 118.8 (10287) 144.4 (102816) 1.1 (121017) 11.5 (321017) 153.3 (821017) 63.7 (2345) 4.8 (23412) 177.3 (11345) 172.3 (113412) 0.2 (3451) 8.1 (3456) 96.2 (34513) 139.9 (12451) 179.1 (12456) 76.5 (124513) 47.3 (1567) 7.8 (15614) 176.6 (4567) 97.5 (45614) 78.0 (13567) 138.3 (135614) 46.1 (151322) 62.6 (151323) 58.5 (151324) 178.0 (451322) 62.2 (451323) 176.7 (451324) 57.2 (651322) 174.8 (651323) 64.2 (651324) 55.3 (5678) 5.0 (56715) 172.1 (14678) 179.7 (146715) 3.2 (561418) 40.2 (761418) 145.0 (6781) 0.5 (6782) 54.1 (67816) 170.7 (15781) 177.6 (15782) 123.0 (157816) 12.2

Frequencies(cm1_):_{207.5 78.6 107.7 136.8 139.8 192.0 226.7 242.5}

(18)

2,6Dicyano4,8diphenylsemibullvalene (10d) X Y Z

C1 0.333295 0.711633 1.031822 C2 1.496177 0.528676 0.073742 C3 1.532645 0.771078 0.416743 C4 0.568985 1.585841 0.186459 C5 0.333295 0.711633 1.031822 C6 1.496177 0.528676 0.073742 C7 1.532645 0.771078 0.416743 C8 0.568985 1.585841 0.186459

X Y Z C20 1.145172 5.125181

0.983752

C21 0.333295 5.847542 0.103111

C22 0.420028 5.165773 0.853301

C23 0.362950 3.777457 0.934094

H24 1.832533 3.198633 1.607325

H25 1.728341 5.645821 1.738286

H26 0.283673 6.930665 0.168972

H27 1.061530 5.715204 1.536275

H9 0.597089 1.097385 2.020721 C10 2.429965 1.536510 0.253818 H11 2.261936 1.102350 1.146514 C12 0.458025 3.030750 0.062067 H13 0.597089 1.097385 2.020721 C14 2.429965 1.536510 0.253818 H15 2.261936 1.102350 1.146514 C16 0.458025 3.030750 0.062067 N17 3.223876 2.358648 0.492439 N18 3.223876 2.358648 0.492439 C19 1.205774 3.739964 0.905695

H28 0.963816 3.269886 1.680976

C29 1.205774 3.739964 0.905695

C30 1.145172 5.125181 0.983752

C31 0.333295 5.847542 0.103111

C32 0.420028 5.165773 0.853301

C33 0.362950 3.777457 0.934094

H34 1.832533 3.198633 1.607325

H35 1.728341 5.645821 1.738286

H36 0.283673 6.930665 0.168972

H37 1.061530 5.715204 1.536275

H38 0.963816 3.269886 1.680976

(19)

(122322) 121.0 (122328) 120.0 (222328) 118.9 (313237) 120.2 (333237) 119.5 (163338) 120.0 (323338) 118.9

(5123) 0.2 (51210) 179.0 (8123) 108.8 (81210) 72.4 (9123) 125.5 (91210) 53.4 (2154) 4.8 (2156) 99.4 (21513) 134.6 (8154) 109.1 (81513) 121.1 (91513) 8.7 (2187) 98.0 (21816) 83.4 (5187) 8.0 (51816) 170.5 (9187) 137.0 (91816) 41.6 (1234) 5.2 (12311) 177.5 (10234) 173.7 (102311) 3.7 (121017) 87.1 (321017) 91.6 (2345) 8.4 (23412) 170.2 (11345) 174.4 (113412) 7.1 (341219) 11.7 (341223) 166.1 (541219) 170.0 (541223) 12.3 (561418) 87.1 (761418) 91.6 (4121920) 177.1 (4121924) 3.5 (23121920) 0.7 (23121924) 178.7 (4122322) 177.0 (4122328) 3.1 (19122322) 0.8 (19122328) 179.1 (8163338) 3.1 (29163338) 179.1 (12192021) 0.3 (12192025) 179.9 (24192021) 179.2 (24192025) 0.4 (19202122) 0.2 (19202126) 179.7 (25202122) 179.4 (25202126) 0.1 (20212223) 0.2 (20212227) 179.4 (26212223) 179.7 (26212227) 0.1 (21222312) 0.4 (21222328) 179.5 (27222312) 179.9 (27222328) 0.0 (30313237) 179.4 (36313237) 0.1 (31323338) 179.5 (37323316) 179.9 (37323338) 0.0

(bond)(plane) angle (113)(234) 2.3

_{25.6 41.5 47.2 57.1 67.8 103.3 107.9 114.2}

152.7 177.0 182.3 217.5 230.8 277.2 330.2 338.8 355.4 377.1 410.9 411.1 443.7 464.1 475.0 485.3 553.2 580.1 587.3 594.5 596.3 625.7 631.8 632.1 644.4 659.0 697.6 698.2 704.5 780.8 781.2 842.1 842.4 867.8 873.5 885.4 898.6 922.2 922.7 924.0 925.8 951.4 965.0 965.2 996.8 996.9 1013.4 1013.6 1016.6 1021.5 1061.0 1061.1 1117.9 1118.5 1182.9 1192.0 1196.5 1197.7 1224.7 1224.9 1247.4 1253.4 1255.6 1257.0 1291.2 1299.6 1316.5 1316.6 1352.2 1357.9 1380.6 1381.2 1458.4 1462.6 1498.3 1501.5 1504.8 1544.4 1550.7 1550.8 1627.4 1628.0 1655.3 1656.4 2305.0 2306.7 3083.2 3095.4 3188.6 3188.6 3197.3 3197.3 3207.5 3207.6 3214.5 3214.5 3221.7 3221.9 3241.3 3241.6

(20)

X Y Z C1 0.669096 0.163995 1.225252 C2 0.707452 1.199049 0.147698 C3 0.699394 1.422686 0.288315 C4 1.532173 0.561465 0.284733 C5 0.719605 0.488554 1.057575 C6 0.439137 1.567525 0.008698 C7 0.695692 1.321088 0.631458 C8 1.440642 0.199521 0.005694 H9 1.116499 0.319344 2.189541 C10 1.555451 2.370340 0.257695 H11 0.969528 2.210737 0.964505 C12 2.997592 0.474553 0.090881 H13 1.172051 0.856333 1.967203 C14 1.377311 2.597502 0.340218 H15 1.065249 1.857369 1.484270 C16 2.940333 0.236440 0.065951 N17 2.189944 3.309532 0.329611 N18 2.115262 3.424897 0.590723 C19 3.578760 0.787596 1.136257

X Y Z C20 4.951489 0.741609

1.300136

C21 5.767614 0.375330 0.241840

C22 5.201608 0.053439 0.980359

C23 3.827990 0.099231 1.143888

H24 2.952776 1.049521 1.969528

H25 5.382239 0.980956 2.255680

H26 6.834073 0.333933 0.371047

H27 5.827201 0.234196 1.805976

H28 3.405917 0.145097 2.101912

C29 3.599804 0.213240 1.204720

C30 4.977366 0.127562 1.298877

C31 5.713133 0.410115 0.254142

C32 5.064410 0.862658 0.881767

C33 3.684108 0.777828 0.973902

H34 3.034812 0.641671 2.013785

H35 5.475547 0.485297 2.181723

H36 6.784026 0.473004 0.325324

H37 5.628751 1.281715 1.695297

H38 3.187245 1.139369 1.856340

(12) 1.495 (15) 1.544 (18) 1.488 (19) 1.074 (23) 1.490 (28) 1.585 (210) 1.450 (34) 1.328 (311) 1.073 (45) 1.536 (412) 1.481 (56) 1.531 (513) 1.080 (67) 1.326 (614) 1.436 (78) 1.490 (715) 1.073 (816) 1.502 (1017) 1.136 (1219) 1.393 (1223) 1.393 (1418) 1.137 (1629) 1.391 (1633) 1.388 (1920) 1.383 (1924) 1.075 (2021) 1.386 (2025) 1.075 (2122) 1.385 (2126) 1.075 (2223) 1.384 (2227) 1.075 (2328) 1.075 (2930) 1.383 (2934) 1.076 (3031) 1.386 (3035) 1.075 (3132) 1.384 (3136) 1.075 (3233) 1.386 (3237) 1.075 (3338) 1.075

(21)

(1513) 115.4 (456) 103.5 (4513) 115.8 (6513) 114.4 (567) 110.9 (5614) 123.5 (7614) 125.1 (678) 111.2 (6715) 125.8 (8715) 123.0 (182) 58.1 (187) 106.0 (1816) 124.2 (287) 118.1 (2816) 119.2 (7816) 117.4 (21017) 178.0 (41219) 121.0 (41223) 120.5 (191223) 118.5 (61418) 178.5 (81629) 120.3 (81633) 120.6 (291633) 119.0 (121920) 120.7 (121924) 119.6 (201924) 119.6 (192021) 120.2 (192025) 119.7 (212025) 120.1 (202122) 119.7 (202126) 120.2 (222126) 120.2 (212223) 120.1 (212227) 120.1 (232227) 119.7 (122322) 120.8 (122328) 120.1 (222328) 119.2 (162930) 120.5 (162934) 119.7 (302934) 119.8 (293031) 120.1 (293035) 119.8 (313035) 120.1 (303132) 119.8 (303136) 120.1 (323136) 120.1 (313233) 120.1 (313237) 120.2 (333237) 119.8 (163332) 120.5 (163338) 119.9 (323338) 119.6

(22)

(29303136) 179.7 (35303132) 179.7 (35303136) 0.2 (30313233) 0.0 (30313237) 179.9 (36313233) 179.8 (36313237) 0.2 (31323316) 0.2 (31323338) 179.5 (37323316) 179.8 (37323338) 0.5

_{30.4 36.4 40.1 55.3 72.4 97.6 116.9 126.0}

167.1 198.0 204.8 255.8 300.4 315.2 366.4 375.4 402.5 440.5 453.7 454.5 485.5 519.4 540.0 568.9 607.6 627.8 630.4 650.1 676.8 679.8 700.5 729.4 748.4 765.4 774.8 780.3 801.4 859.8 864.6 885.9 934.8 943.3 954.7 957.4 985.5 1005.8 1018.1 1034.7 1047.7 1049.6 1060.2 1078.4 1090.1 1091.0 1101.1 1102.6 1128.9 1129.4 1130.7 1134.4 1158.7 1184.5 1188.9 1209.8 1216.6 1223.3 1236.6 1291.1 1302.7 1306.3 1324.3 1330.0 1342.8 1354.8 1359.9 1414.6 1423.8 1440.6 1464.5 1474.4 1481.9 1526.6 1611.7 1613.0 1670.4 1674.3 1776.6 1782.2 1806.4 1811.3 1828.8 1839.6 2603.7 2609.8 3299.7 3358.2 3360.0 3362.9 3367.4 3372.5 3377.5 3379.4 3383.1 3385.7 3393.0 3394.0 3409.9 3415.7

2,6Dicyano4,8diphenylsemibullvalene (10d) X Y Z

C1 0.309832 0.715134 1.148197 C2 1.423254 0.585871 0.151743 C3 1.482942 0.688353 0.369178 C4 0.557671 1.527061 0.230494 C5 0.309832 0.715134 1.148197 C6 1.423254 0.585871 0.151743 C7 1.482942 0.688353 0.369178 C8 0.557671 1.527061 0.230494 H9 0.560968 1.128499 2.114347 C10 2.361304 1.618032 0.153152 H11 2.178587 0.984442 1.129602 C12 0.480487 2.985594 0.052791 H13 0.560968 1.128499 2.114347 C14 2.361304 1.618032 0.153152 H15 2.178587 0.984442 1.129602

X Y Z C20 0.895724 4.958565

1.277531

C21 0.434593 5.763982 0.246476

C22 0.009566 5.182867 0.928316

C23 0.009566 3.806898 1.075796

H24 1.253522 2.974732 1.948055

H25 1.230372 5.400606 2.198581

H26 0.414667 6.832413 0.362841

H27 0.374343 5.797946 1.730841

H28 0.338118 3.377845 1.997060

C29 0.915496 3.585758 1.131375

C30 0.895724 4.958565 1.277531

C31 0.434593 5.763982 0.246476

C32 0.009566 5.182867 0.928316

C33 0.009566 3.806898 1.075796

(23)

C16 0.480487 2.985594 0.052791 N17 3.132746 2.423630 0.380130 N18 3.132746 2.423630 0.380130 C19 0.915496 3.585758 1.131375

H35 1.230372 5.400606 2.198581

H36 0.414667 6.832413 0.362841

H37 0.374343 5.797946 1.730841

H38 0.338118 3.377845 1.997060

(12) 1.500 (15) 1.559 (18) 1.501 (19) 1.080 (23) 1.378 (210) 1.428 (34) 1.385 (311) 1.072 (412) 1.471 (1018) 1.138 (1219) 1.397 (1223) 1.394 (1417) 1.138 (1920) 1.381 (1924) 1.075 (2021) 1.387 (2025) 1.075 (2122) 1.384 (2126) 1.075 (2223) 1.384 (2227) 1.075 (2328) 1.074 (3237) 1.075 (3338) 1.074 (2,8) 2.195 (215) 102.5 (218) 94.0 (219) 117.0 (518) 105.5 (519) 116.3 (819) 118.3 (123) 111.3 (1210) 124.6 (3210) 124.0 (234) 111.5 (2311) 123.5 (4311) 125.0 (345) 108.9 (3412) 125.7 (5412) 125.4 (21018) 178.3 (41219) 120.8 (41223) 120.9 (191223) 118.3 (61417) 178.3 (121920) 120.8 (121924) 119.9 (201924) 119.3 (192021) 120.2 (192025) 119.7 (212025) 120.1 (202122) 119.6 (202126) 120.2 (222126) 120.2 (212223) 120.2 (212227) 120.2 (232227) 119.6 (122322) 120.8 (122328) 120.2 (222328) 119.0 (313237) 120.2 (333237) 119.6 (163338) 120.2 (323338) 119.0

(5123) 0.0 (51210) 175.9 (8123) 106.8 (81210) 77.3 (9123) 128.5 (91210) 47.4 (2154) 3.5 (2156) 94.2 (21513) 136.8 (8154) 101.3 (81513) 125.4 (91513) 7.8 (2187) 98.1 (21816) 84.8 (5187) 6.0 (51816) 171.1 (9187) 138.2 (91816) 38.9 (1234) 3.9 (12311) 177.3 (10234) 172.0 (102311) 6.8 (121018) 108.1 (321018) 67.3 (2345) 6.3 (23412) 170.8 (11345) 174.9 (113412) 8.0 (341219) 28.5 (341223) 149.5 (541219) 154.9 (541223) 27.1 (561417) 108.1 (761417) 67.3 (4121920) 177.3 (4121924) 3.9 (23121920) 0.8 (23121924) 178.0 (4122322) 177.2 (4122328) 2.3 (19122322) 0.9 (19122328) 179.6 (8163338) 2.3 (29163338) 179.6 (12192021) 0.3 (12192025) 179.7 (24192021) 178.5 (24192025) 0.8 (19202122) 0.2 (19202126) 179.7 (25202122) 179.2 (25202126) 0.3 (20212223) 0.2 (20212227) 179.6 (26212223) 179.7 (26212227) 0.1 (21222312) 0.3 (21222328) 179.9 (27222312) 179.8 (27222328) 0.3 (30313237) 179.6 (36313237) 0.1 (31323338) 179.9 (37323316) 179.8 (37323338) 0.3

(bond)(plane) angle (113)(234) 1.0

_{264.0 31.5 39.7 42.4 56.2 73.6 104.4 119.3}

(24)

(25)

11

X Y Z C1 0.000000 0.784523

1.049797

C2 1.140702 1.145241 0.119638

C3 1.703224 0.000000 0.439946

C4 1.140702 1.145241 0.119638

C5 0.000000 0.784523 1.049797

C6 1.140702 1.145241 0.119638

C7 1.703224 0.000000 0.439946

C8 1.140702 1.145241 0.119638

H9 0.000000 1.273555 2.025625

C10 1.565107 2.470217 0.131683

H11 2.481557 0.000000 1.193645

C12 1.565107 2.470217 0.131683

H13 0.000000 1.273555 2.025625

C14 1.565107 2.470217 0.131683

H15 2.481557 0.000000 1.193645

C16 1.565107 2.470217 0.131683

N17 1.931574 3.562553 0.310467

N18 1.931574 3.562553 0.310467

N19 1.931574 3.562553 0.310467

N20 1.931574 3.562553 0.310467

(12) 1.515 (15) 1.569 (19) 1.092 (23) 1.393 (210) 1.414 (311) 1.083 (1017) 1.166 (2,8) 2.281

(215) 103.8 (218) 97.7 (219) 116.2 (519) 116.6 (123) 110.8 (1210) 123.9 (3210) 125.3 (234) 110.6 (2311) 124.7 (21017) 178.4

(26)

(bond)(plane) angle (113)(234) 0.8

(27)

11

X Y Z C1 0.000000 0.779250

1.084341

C2 1.084742 1.130613 0.111219

C3 1.631515 0.000000 0.460326

C4 1.084742 1.130613 0.111219

C5 0.000000 0.779250 1.084341

C6 1.084742 1.130613 0.111219

C7 1.631515 0.000000 0.460326

C8 1.084742 1.130613 0.111219

H9 0.000000 1.282315 2.039228

C10 1.542353 2.462682 0.132776

H11 2.367526 0.000000 1.239789

C12 1.542353 2.462682 0.132776

H13 0.000000 1.282315 2.039228

C14 1.542353 2.462682 0.132776

H15 2.367526 0.000000 1.239789

C16 1.542353 2.462682 0.132776

N17 1.928454 3.517561 0.306060

N18 1.928454 3.517561 0.306060

N19 1.928454 3.517561 0.306060

N20 1.928454 3.517561 0.306060

(12) 1.499 (15) 1.558 (19) 1.079 (23) 1.380 (210) 1.429 (311) 1.072 (1017) 1.137 (2,8) 2.169

(215) 103.6 (218) 92.7 (219) 117.7 (519) 117.8 (123) 111.3 (1210) 124.1 (3210) 124.5 (234) 110.0 (2311) 125.0 (21017) 178.5

(28)

(bond)(plane) angle (113)(234) 0.4

(29)

15

X Y Z C1 0.714448 0.000007

1.111277

C2 1.161475 0.793061 0.070564

C3 0.017596 1.558071 0.561380

C4 1.103837 1.206093 0.110716

C5 0.828143 0.000009 1.012829

C6 1.103841 1.206087 0.110738

C7 0.017623 1.558024 0.561417

C8 1.161463 0.793046 0.070589

H9 1.236859 0.000023 2.048989

C10 2.452280 1.450494 0.113937

H11 0.042406 2.292668 1.340018

C12 2.418290 1.746680 0.092943

H13 1.359735 0.000013 1.952708

C14 2.418296 1.746676 0.092899

H15 0.042360 2.292600 1.340075

C16 2.452258 1.450502 0.113989

N17 3.449371 1.989885 0.154514

N18 3.461325 2.175641 0.226039

N19 3.461321 2.175634 0.226110

N20 3.449321 1.989943 0.154574

(12) 1.492 (15) 1.546 (19) 1.073 (23) 1.489 (28) 1.586 (210) 1.449 (34) 1.325 (311) 1.072 (45) 1.531 (412) 1.436 (513) 1.080 (1017) 1.134 (1219) 1.136

(215) 104.4 (218) 64.2 (219) 123.1 (519) 122.8 (123) 107.3 (128) 57.9 (1210) 122.1 (328) 120.9 (3210) 117.5 (8210) 117.0 (234) 110.2 (2311) 123.2 (4311) 126.6 (345) 111.1 (3412) 125.4 (5412) 123.0 (154) 102.5 (1513) 115.8 (456) 103.9 (4513) 115.1 (21017) 178.5 (41219) 178.6

(30)

(9128) 114.2 (91210) 10.4 (2154) 20.5 (2156) 87.1 (21513) 146.7 (9154) 126.2 (91513) 0.0 (1234) 5.8 (12311) 173.3 (8234) 56.6 (82311) 124.2 (10234) 148.1 (102311) 31.1 (1287) 91.9 (12816) 112.6 (3287) 0.0 (32816) 155.5 (102816) 0.0 (121017) 126.8 (321017) 9.5 (821017) 165.8 (2345) 8.3 (23412) 179.6 (11345) 172.6 (113412) 0.5 (3451) 18.4 (3456) 88.2 (34513) 145.0 (12451) 169.3 (12456) 84.1 (124513) 42.7 (341219) 136.9 (541219) 51.9

_{70.5 88.0 119.4 120.3 128.9 147.7 212.8 226.4}

316.4 349.4 444.1 444.3 467.3 482.2 526.5 532.4 566.5 576.1 626.6 632.3 663.9 689.7 756.2 770.3 796.6 890.8 953.0 965.7 997.9 1025.7 1028.5 1038.6 1132.2 1189.4 1200.5 1246.4 1269.7 1330.5 1346.5 1419.4 1425.1 1431.8 1459.6 1514.2 1834.6 1837.2 2614.6 2615.8 2624.5 2626.0 3317.6 3399.4 3431.2 3431.6