Bicalicene

{{Chembox

| Name = trans-Bicalicene

| ImageFile = Trans-Bicalicene.svg

| ImageSize = 200px

| IUPACName = (4aZ,8aZ)-Dicyclopenta[a,e]dicyclopropa[c,g][8]annulene
Dicyclopenta[a,e]dicyclopropa[c,g]cyclooctene

| OtherNames =

| Section1 = {{Chembox Identifiers

| CASNo = 73091-52-8

| CASNo_Ref = {{cascite|correct|CAS}}

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = 494N9YP93C

| PubChem = 5257656

| ChemSpiderID = 4423214

| SMILES = C1=CC2=C3C=C3C4=CC=CC4=C5C=C5C2=C1

| InChI = 1/C16H8/c1-3-9-10(4-1)14-8-16(14)12-6-2-5-11(12)15-7-13(9)15/h1-8H/b13-9-,14-10-,15-11-,16-12-

| InChIKey = FVDGMBFXSFSQOU-NONDJZLBBM

| StdInChI = 1S/C16H8/c1-3-9-10(4-1)14-8-16(14)12-6-2-5-11(12)15-7-13(9)15/h1-8H/b13-9-,14-10-,15-11-,16-12-

| StdInChIKey = FVDGMBFXSFSQOU-NONDJZLBSA-N

}}

| Section2 = {{Chembox Properties

| C=16|H=8

| Appearance =

| Density =

| MeltingPt = 125–130 °C ({{abbr|dec|decomposes}}){{cite journal | last1 = Yonedo | first1 = Shigeo | last2 = Shibata | first2 = Mitsuhiro | last3 = Kida | first3 = Shuji | last4 = Yoshida | first4 = Zen-ichi | last5 = Kai | first5 = Yasusi | last6 = Miki | first6 = Kunio | last7 = Kasai | first7 = Nobutami | name-list-style = vanc | title = A Novel Aromatic Hydrocarbon with 16 π-Electron Periphery: "Cyclic Bicalicene" | journal = Angewandte Chemie International Edition in English | date = January 1984 | volume = 23 | issue = 1 | pages = 63–64 | doi = 10.1002/anie.198400631}}

| BoilingPt =

| Solubility =

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| Section3 = {{Chembox Hazards

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{{Chembox

| Name = cis-Bicalicene

| ImageFile = Cis-Bicalicene.svg

| ImageSize = 200px

| IUPACName = Dicyclopenta[a,c]dicyclopropa[e,g]cyclooctene

| OtherNames =

| Section1 = {{Chembox Identifiers

| CASNo = 122605-73-6

| PubChem = 101619525

| ChemSpiderID =

| SMILES = C1=CC2=C3C=C3C4=CC4=C5C=CC=C5C2=C1

| StdInChI=1S/C16H8/c1-3-9-10-4-2-6-12(10)14-8-16(14)15-7-13(15)11(9)5-1/h1-8H

| StdInChIKey = MIGVZWUAYKWALJ-UHFFFAOYSA-N

}}

| Section2 = {{Chembox Properties

| C=16|H=8

| Appearance =

| Density =

| MeltingPt =

| BoilingPt =

| Solubility =

}}

| Section3 = {{Chembox Hazards

| MainHazards =

| FlashPt =

| AutoignitionPt =

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Bicalicene is polycyclic hydrocarbon with chemical formula C16H8, composed of two cyclopentadiene and two cyclopropene rings linked into a larger eight-membered ring. There are two isomers: cis-bicalicene and trans-bicalicene. It is a dimer of calicene.

Synthesis

Bicalicene is prepared by treatment of 1,2-bis(tert-butylthio)-3,3-dichlorocyclopropene with cyclopentadiene anion, followed by desulfurizing stannylation with tributyltin hydride, and then treatment with silica gel.

Properties

File:Trans-Bicalicene aromatics colored.png

trans-Bicalicene is polycyclic aromatic hydrocarbon, which is unusual for a 16 π electron ring system. Viewed as a unified ring structure, Hückel's rule predicts it would be anti-aromatic (4n π electrons). Instead, however, the structure has a dominant partially-delocalized charge-separated structure consisting of four independently-aromatic (4n+2 π electron) rings: two as cyclopropenyl cations (two π electrons each) and two as cyclopentadienyl anions (six π electrons each).{{cite journal | vauthors = Oziminski WP, Palusia M | title = Capturing the elusive aromaticity of bicalicene | journal = Physical Chemistry Chemical Physics | year = 2013 | volume = 15 | issue = 9 | pages = 3286–3293| doi = 10.1039/C2CP43426A | pmid = 23358331 | bibcode = 2013PCCP...15.3286O }}

cis-Bicalicene, by contrast, is an antiaromatic hydrocarbon.{{cite journal |author=Jelena Đurđević Nikolić |author2=Ivan Gutman | title = A Comparative Study of the Two Isomers of Bicalicene | journal = Polycyclic Aromatic Compounds | year = 2016 |volume=38 | pages = 1–7 | doi = 10.1080/10406638.2016.1140659 |s2cid=99213944 }} A resonance structure with four aromatic rings, analogous to the one that makes the trans isomer stable, would suffer from destabilizing charge effects, and other resonance structures have 4n rather than 4n+2 π electrons in at least one ring.

References