Overcrowded naphthologues of mono-bridged tetraarylethylenes -
analogues of bistricyclic aromatic enes
Naela Assadi, Sergei Pogodin, Shmuel Cohen, Amalia Levy and Israel Agranat*
Supporting Information
Table S1. The B3LYP/6-31G(d) total and relative energies of enes 4–8 and 20.
[a] / ETot / ΔETot / ω[b] / τ[c]Hartree / kJ/mol / deg / deg
t–5 / C2 / M / –1308.89813038 / 16.8 / 9.7 / –71.9
[f–5] / Cs / TS / –1308.89177767 / 33.5 / 0.0 / –84.3
84.3
t–7 / C2 / M / –1308.90451950 / 0.0 / 20.1 / –133.1
[f–7] / Cs / TS / –1308.90065989 / 10.1 / 0.0 / 93.7
–93.7
tf–6 / C1 / M / –1384.10413941 / 13.4 / 6.4 / –67.0
–91.1
ft–6 / C1 / M / –1384.10231309 / 18.1 / 14.7 / 105.1
–57.8
[f–6] / Cs / TS / –1384.09979958 / 24.7 / 0.0 / 75.4
–75.4
[t–6] / C2 / TS / –1384.09571124 / 35.5 / 31.6 / –130.1
tf–8 / C1 / M / –1384.10922488 / 0.0 / 10.3 / –53.5
–89.7
ft–8 / C1 / M / –1384.10913492 / 0.2 / 9.9 / –53.2
93.6
[f–8] / Cs / TS / –1384.10856566 / 1.7 / 0.0 / 71.9
–71.9
[t–8] / C2 / TS / –1384.10595817 / 8.6 / 31.1 / –49.8
t–4 / C2 / M / –1001.61615215 / 0.0 / 18.7 / 54.3
t–4 / Cs / TS / –1001.61277138 / 8.9 / 0.0 / 91.5
–91.5
t–20 / C2 / M / –1230.66288990 / – / 22.0 / –49.4
[a] M=minimum, TS=transition state. [b] The average of C9a–C9–C9'–C1'(C2') and C8a–C9–C9'–C1''(C2''). [c] the C9–C9'–C1'–C8a' (C9–C9'–C2''–C1') torsion angles.
Table S2. The B3LYP/6-31G(d) relative energies and characteristic geometrical parameters of enes 4–8 and 20.
[a] / ΔETot / ΔH298 / ΔG298 / ω[c] / τ[d] / θ[e] / φ[f] / ν[g] / C1...C1' / H1...C1' / H1...C8a' / H2''...C8' / C1...C2' / H1...C2'kJ/ / kJ/ / kJ/ / deg / deg / deg / deg / deg / C8...C1'' / H8...C1'' / H8...C8a'' / H2'...C8'' / C8...C2'' / H8...C2''
mol[b] / mol[b] / mol[b] / pm / pm / pm / pm / pm / pm
t–5 / C2 / M / 16.8 / 17.0 / 16.1 / 9.7 / –71.9 / 80.6 / 1.0 / 77.2 / 314.7 / 251.9 / 271.1 / 274.7
5 X–ray / – / – / – / – / – / 4.6 / 68.5 / 72.3 / 2.4 / 69.6 / 314.6 / 256.4 / 262.3 / 233.7
86.2 / 90.3 / 306.9 / 248.9 / 278.3 / 286.6
ft–5 / C1 / M / 18.9 / 19.0 / 19.0 / 16.4 / 60.9 / 88.8 / 1.6 / 69.9 / 313.8 / 253.5 / 292.6 / 299.0
–121.3 / 75.2 / 318.7 / 256.6 / 263.8 / 251.6
[f–5] / Cs / TS / 33.5 / 31.0 / 37.7 / 0.0 / –84.3 / 75.6 / 2.9 / 78.7 / 313.4 / 250.1 / 264.8 / 218.5
84.3 / 200.1
t–7 / C2 / M / 0.0 / 0.0 / 0.0 / 20.1 / –133.1 / 76.1 / 1.8 / 64.5 / 318.4 / 258.5
ft–7 / C1 / M / –0.4 / –0.5 / –2.7 / 19.8 / 54.4 / 78.0 / 1.9 / 63.0 / 318.7 / 259.0
–134.1 / 68.2 / 319.1 / 258.8
[f–7] / Cs / TS / 10.1 / 7.3 / 10.3 / 0.0 / 93.7 / 71.3 / 0.2 / 88.1 / 313.0 / 249.9
–93.7
tf–6 / C1 / M / 13.4 / 14.1 / 19.0 / 6.4 / –67.0 / 79.0 / 29.7 / 49.0 / 304.6 / 259.6 / 326.5 / 239.1
–91.1 / 65.8 / 308.5 / 258.4 / 250.5 / 262.1
6 X–ray / – / – / – / – / – / 2.8 / 67.7 / 75.1 / 35.5 / 42.5 / 302.6 / 262.0 / 312.7 / 233.3
97.1 / 66.4 / 312.9 / 270.7 / 262.7 / 258.6
ft–6 / C1 / M / 18.1 / 18.6 / 23.6 / 14.7 / 105.1 / 82.0 / 29.8 / 45.0 / 305.1 / 261.2 / 321.5 / 259.3
–57.8 / 68.7 / 308.5 / 250.8 / 322.1 / 231.4
[f–6] / Cs / TS / 24.7 / 22.9 / 35.8 / 0.0 / 75.4 / 72.3 / 31.9 / 49.9 / 305.0 / 256.2 / 317.9 / 209.6
–75.4 / 202.7
[t–6] / C2 / TS / 35.5 / 33.3 / 47.1 / 31.6 / –130.1 / 78.9 / 3.8 / 77.0 / 297.4 / 230.1 / 262.9 / 271.0
tf–8 / C1 / M / 0.0 / 0.0 / 0.0 / 10.3 / –53.5 / 81.3 / 30.7 / 42.0 / 306.9 / 264.0
–89.7 / 63.9 / 308.3 / 255.3
ft–8 / C1 / M / 0.2 / 0.3 / 1.3 / 9.9 / –53.2 / 79.9 / 30.8 / 41.2 / 307.4 / 263.9
93.6 / 62.9 / 306.4 / 253.2
[f–8] / Cs / TS / 1.7 / –0.8 / 8.8 / 0.0 / 71.9 / 70.2 / 31.1 / 49.9 / 304.8 / 256.9
–71.9
[t–8] / C2 / TS / 8.6 / 6.1 / 17.9 / 31.1 / –49.8 / 72.7 / 3.7 / 71.6 / 299.9 / 231.8
C1...C1' / H1...C1' / H1...C2' / H2''...C2'
C8...C1'' / H8...C1'' / H8...C2'' / H2'...C2''
t–4 / C2 / – / – / – / – / 18.7 / –54.3 / 80.3 / 1.8 / 66.5 / 318.3 / 257.9 / 324.1 / 355.2
4 X–ray / C1 / – / – / – / – / 1.8 / 74.0 / 74.1 / 3.8 / 70.3 / 314.6 / 258.2 / 263.9 / 279.5
80.3 / 82.5 / 310.1 / 255.1 / 265.5 / 297.6
t–20 / C2 / – / – / – / – / 22.0 / 49.4 / 74.6 / 2.1 / 64.4 / 319.7 / 260.2 / 266.0 / 337.0
20 X–ray / 12.4 / 64.8 / 86.2 / 6.1 / 64.8 / 333.4 / 277.2 / 250.8 / 384.7
54.4 / 69.2 / 315.0 / 258.2 / 292.9 / 541.2
[a] M=minimum, TS=transition state. [b] The energies of the 1-naphthyl derivatives 5 and 6 are given relatively to the energies of the 2-naphthyl derivatives 7 and 8, respectively. [c] The average of C9a–C9–C9'–C1' (C2') and C8a–C9–C9'–C1'' (C2''). [d] The C9–C9'–C1'–C8a' (C9–C9'–C2''–C1') torsion angles. [e] The dihedral angle between planes DE and FG, Fig. 2. [f] The dihedral angle between planes A and B, Fig. 2. [g] The dihedral angle between planes ABC and DE (FG), Fig. 2.
Table S3. Total energies at B3LYP/6-31G(d) and Z-matrices/Cartesian coordinates of the minima conformations of enes under study.
t–5, Total energy=–1308.89813038 Hartree
C
C 1 r21
X 1 1. 2 90.
X 2 1. 1 90. 3 d4213 0
C 1 r51 2 a512 3 d5123 0
C 1 r51 2 a512 3 -d5123 0
C 2 r72 1 a721 4 d7214 0
C 2 r72 1 a721 4 -d7214 0
C 5 r95 1 a951 2 d9512 0
C 6 r95 1 a951 2 d9512 0
C 7 r117 2 a1172 1 d11721 0
C 8 r117 2 a1172 1 d11721 0
C 5 r135 9 a1359 1 d13591 0
C 6 r135 10 a1359 1 d13591 0
C 7 r157 11 a15711 2 d157112 0
C 8 r157 12 a15711 2 d157112 0
C 13 r1713 5 a17135 9 d171359 0
C 14 r1713 6 a17135 10 d171359 0
C 15 r1915 7 a19157 11 d1915711 0
C 16 r1915 8 a19157 12 d1915711 0
C 17 r2117 13 a211713 5 d2117135 0
C 18 r2117 14 a211713 6 d2117135 0
C 19 r2319 15 a231915 7 d2319157 0
C 20 r2319 16 a231915 8 d2319157 0
C 21 r2521 17 a252117 13 d25211713 0
C 22 r2521 18 a252117 14 d25211713 0
C 23 r2723 19 a272319 15 d27231915 0
C 24 r2723 20 a272319 16 d27231915 0
H 13 r2913 5 a29135 9 d291359 0
H 14 r2913 6 a29135 10 d291359 0
H 15 r3115 7 a31157 11 d3115711 0
H 16 r3115 8 a31157 12 d3115711 0
H 17 r3317 13 a331713 5 d3317135 0
H 18 r3317 14 a331713 6 d3317135 0
H 19 r3519 15 a351915 7 d3519157 0
H 20 r3519 16 a351915 8 d3519157 0
H 21 r3721 17 a372117 13 d37211713 0
H 22 r3721 18 a372117 14 d37211713 0
H 23 r3923 19 a392319 15 d39231915 0
H 24 r3923 20 a392319 16 d39231915 0
H 25 r4125 21 a412521 17 d41252117 0
H 26 r4125 22 a412521 18 d41252117 0
C 27 r4327 23 a432723 19 d43272319 0
C 28 r4327 24 a432723 20 d43272319 0
C 11 r4511 7 a45117 2 d451172 0
a252117=120.21581754
a272319=120.55972148
a29135=121.23040035
a31157=119.20280474
a331713=119.25707305
a351915=119.4036501
a372117=119.91254109
a392319=120.66538515
a412521=120.36955338
a432723=121.28703918
a45117=123.01985166
a474327=121.08612089
a494511=121.17104551
a554327=118.43560755
a574511=118.90010949
a594743=120.25001529
a614945=119.75424327
d4213=170.32961938
d9512=-179.65873671
d11721=-71.85382659
d13591=-177.12207628
d157112=-184.19323414
d171359=-1.16892633
d1915711=2.19626424
d2117135=0.29788336
d2319157=-1.37829644
d25211713=0.54938769
d27231915=-0.20839794
d291359=178.62299456
d3115711=181.74468683
d3317135=-179.694771
d3519157=-181.16199665
d37211713=-179.87474974
d39231915=-179.71125009
d41252117=179.10146034
d43272319=181.05146596
d451172=2.18030236
d47432711=-0.28970656
d4945117=180.47138215
d55432711=179.9141984
d5745117=0.67950595
d59474327=180.09937652
d61494511=179.9846363
d5123=90.
d7214=90.
t–7, Total energy=–1308.90451950 Hartree
C
C 1 r21
X 1 1. 2 90.
X 2 1. 1 90. 3 d4213 0
C 1 r51 2 a512 3 d5123 0
C 1 r51 2 a512 3 -d5123 0
C 2 r72 1 a721 4 d7214 0
C 2 r72 1 a721 4 -d7214 0
C 5 r95 1 a951 2 d9512 0
C 6 r95 1 a951 2 d9512 0
C 7 r117 2 a1172 1 d11721 0
C 8 r117 2 a1172 1 d11721 0
C 5 r135 9 a1359 1 d13591 0
C 6 r135 10 a1359 1 d13591 0
C 7 r157 11 a15711 2 d157112 0
C 8 r157 12 a15711 2 d157112 0
C 13 r1713 5 a17135 9 d171359 0
C 14 r1713 6 a17135 10 d171359 0
C 15 r1915 7 a19157 11 d1915711 0
C 16 r1915 8 a19157 12 d1915711 0
C 17 r2117 13 a211713 5 d2117135 0
C 18 r2117 14 a211713 6 d2117135 0
C 19 r2319 15 a231915 7 d2319157 0
C 20 r2319 16 a231915 8 d2319157 0
C 21 r2521 17 a252117 13 d25211713 0
C 22 r2521 18 a252117 14 d25211713 0
C 23 r2723 19 a272319 15 d27231915 0
C 24 r2723 20 a272319 16 d27231915 0
H 13 r2913 5 a29135 9 d291359 0
H 14 r2913 6 a29135 10 d291359 0
H 15 r3115 7 a31157 11 d3115711 0
H 16 r3115 8 a31157 12 d3115711 0
H 17 r3317 13 a331713 5 d3317135 0
H 18 r3317 14 a331713 6 d3317135 0
H 19 r3519 15 a351915 7 d3519157 0
H 20 r3519 16 a351915 8 d3519157 0
H 21 r3721 17 a372117 13 d37211713 0
H 22 r3721 18 a372117 14 d37211713 0
H 11 r3923 27 a392319 23 d39231915 0
H 12 r3923 28 a392319 24 d39231915 0
H 25 r4125 21 a412521 17 d41252117 0
H 26 r4125 22 a412521 18 d41252117 0
C 23 r4327 19 a432723 15 d43272319 0
C 24 r4327 20 a432723 16 d43272319 0
C 27 r4511 11 a45117 7 d451172 0
a231915=121.11729559
a252117=120.15575344
a272319=118.42645205
a29135=121.20137652
a31157=118.62334688
a331713=119.25925652
a351915=120.06777683
a372117=119.93084234
a392319=118.54729623
a412521=120.35667566
a432723=122.60362718
a45117=122.08389687
a474327=120.76329266
a494511=120.77868806
a554327=118.77904544
a574511=118.72381873
a594743=120.0776397
a614945=120.09143739
d4213=200.10578031
d9512=-180.63955511
d11721=-133.09168176
d13591=-185.50141157
d157112=-183.8771971
d171359=2.33710406
d1915711=0.74820964
d2117135=-0.70009724
d2319157=0.42199949
d25211713=-0.9675797
d27231915=-0.71813355
d291359=182.4947702
d3115711=181.29871615
d3317135=-180.50827433
d3519157=-179.24723621
d37211713=-180.13840877
d39231915=-179.05557381
d41252117=181.69587494
d43272319=179.63605617
d451172=181.01254866
d47432711=0.2079052
d4945117=0.04553467
d55432711=180.12456116
d5745117=0.30057402
d59474327=179.88238261
d61494511=179.99699078
d5123=90.
d7214=90.
tf–6, Total energy=–1384.10413941 Hartree
C
C 1 r21
X 1 1. 2 90.
X 2 1. 1 90. 3 d4213 0
C 1 r51 2 a512 3 d5123 0
C 1 r51a 2 a512a 3 -d5123 0
C 2 r72 1 a721 4 d7214 0
C 2 r72a 1 a721a 4 -d7214 0
C 5 r95 1 a951 2 d9512 0
C 6 r95a 1 a951a 2 d9512a 0
C 7 r117 2 a1172 1 d11721 0
C 8 r117a 2 a1172a 1 d11721a 0
C 5 r135 9 a1359 1 d13591 0
C 6 r135a 10 a1359a 1 d13591a 0
C 7 r157 11 a15711 2 d157112 0
C 8 r157a 12 a15711a 2 d157112a 0
C 13 r1713 5 a17135 9 d171359 0
C 14 r1713a 6 a17135a 10 d171359a 0
C 15 r1915 7 a19157 11 d1915711 0
C 16 r1915a 8 a19157a 12 d1915711a 0
C 17 r2117 13 a211713 5 d2117135 0
C 18 r2117a 14 a211713a 6 d2117135a 0
C 19 r2319 15 a231915 7 d2319157 0
C 20 r2319a 16 a231915a 8 d2319157a 0
C 21 r2521 17 a252117 13 d25211713 0
C 22 r2521a 18 a252117a 14 d25211713a 0
C 23 r2723 19 a272319 15 d27231915 0
C 24 r2723a 20 a272319a 16 d27231915a 0
H 13 r2913 5 a29135 9 d291359 0
H 14 r2913a 6 a29135a 10 d291359a 0
H 15 r3115 7 a31157 11 d3115711 0
H 16 r3115a 8 a31157a 12 d3115711a 0
H 17 r3317 13 a331713 5 d3317135 0
H 18 r3317a 14 a331713a 6 d3317135a 0
H 19 r3519 15 a351915 7 d3519157 0
H 20 r3519a 16 a351915a 8 d3519157a 0
H 21 r3721 17 a372117 13 d37211713 0
H 22 r3721a 18 a372117a 14 d37211713a 0
H 23 r3923 19 a392319 15 d39231915 0
H 24 r3923a 20 a392319a 16 d39231915a 0
H 25 r4125 21 a412521 17 d41252117 0
H 26 r4125a 22 a412521a 18 d41252117a 0
C 27 r4327 23 a432723 19 d43272319 0
C 28 r4327a 24 a432723a 20 d43272319a 0
C 11 r4511 7 a45117 2 d451172 0
d13591=-178.82472838
d13591a=-178.74428267
d157112=-185.2277072
d157112a=-185.13528587
d171359=-3.10626702
d171359a=2.74124952
d1915711=2.52929444
d1915711a=0.48640607
d2117135=0.23134269
d2117135a=-0.0104412
d2319157=-1.16033842
d2319157a=-0.95654016
d25211713=1.85181653
d25211713a=-1.85539558
d27231915=-0.61342428
d27231915a=0.66747353
d291359=177.33120122
d291359a=183.50857011
d3115711=182.18330116
d3115711a=181.05938433
d3317135=-179.69705242
d3317135a=-180.05146342
d3519157=-181.04353432
d3519157a=-180.48588011
d37211713=-179.44672003
d37211713a=-180.54872111
d39231915=-179.94771299
d39231915a=-179.40679635
d41252117=177.87438462
d41252117a=182.03910267
d43272319=181.46498966
d43272319a=179.68125979
d451172=2.11876885
d451172a=6.39317808
d47432711=-0.55444253
d47432711a=0.52745693
d4945117=180.46510235
d4945117a=179.89294909
d55432711=179.74450372
d55432711a=180.29730299
d5745117=0.55111784
d5745117a=0.75165213
d59474327=180.13098238
d59474327a=179.9142072
d61494511=179.94671528
d61494511a=180.1596018
do=181.33361017
ft–6, Total energy=–1384.10231309 Hartree
C -0.2429550449 1.0892606836 -0.6212170589
C 0.2330518538 -0.1900851897 -0.7198962864