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Prismane
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| Preferred IUPAC name
Tetracyclo[2.2.0.02,6.03,5]hexane[1] | |||
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| Properties | |||
| C6H6 | |||
| Molar mass | 78.114 g·mol−1 | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Prismane or Ladenburg benzene is a polycyclic hydrocarbon with the formula C6H6. It is an isomer of benzene, specifically a valence isomer. Prismane is far less stable than benzene. The carbon (and hydrogen) atoms of the prismane molecule are arranged in the shape of a six-atom triangular prism—this compound is the parent and simplest member of the prismanes class of molecules. Albert Ladenburg proposed this structure for the compound now known as benzene.[2] The compound was not synthesized until 1973.[3]
History
[edit]In the mid 19th century, investigators proposed several possible structures for benzene which were consistent with its empirical formula, C6H6, which had been determined by combustion analysis. The first, which was proposed by Friedrich August Kekulé von Stradonitz in 1865, later proved to be closest to the true structure of benzene. This structure inspired several others to draw structures that were consistent with benzene's empirical formula; for example, Albert Ladenburg proposed prismane, James Dewar proposed Dewar benzene, and Koerner and Claus proposed Claus' benzene. Some of these structures would be synthesized in the following years. Prismane, like the other proposed structures for benzene, is still often cited in the literature, because it is part of the historical struggle toward understanding the mesomeric structures and resonance of benzene. Some computational chemists still research the differences between the possible isomers of C6H6.[4]
Properties
[edit]Prismane is a colourless liquid at room temperature.[5] Studying its properties and reactivity is difficult, because all known syntheses have rather low yields.[6]
The deviation of the carbon-carbon bond angle from 109° to 60° in a triangle leads to a high ring strain, reminiscent of that of cyclopropane but greater. The compound is explosive, which is unusual for a hydrocarbon. Due to this ring strain, the bonds have a low bond energy and break at a low activation energy, which makes synthesis of the molecule difficult; Woodward and Hoffmann noted that prismane's thermal rearrangement to benzene is symmetry-forbidden, comparing it to "an angry tiger unable to break out of a paper cage". On account of its strain energy and the aromatic stabilization of benzene, the molecule is estimated to be 90 kcal/mole less stable than benzene, but the activation of this highly exothermic transformation is a surprisingly high 33 kcal/mol, making it persistent at room temperature.[5]
Substituted derivatives appear more stable, probably because of steric hindrance against decomposition.[6]
Synthesis
[edit]
Katz and Acton's original synthesis[3] starts from benzvalene (1) and 4-phenyltriazolidone (2), which is a strong dienophile. The reaction is a stepwise Diels-Alder like reaction, forming a carbocation as intermediate. The adduct (3) is then hydrolyzed under basic conditions and afterwards transformed into a copper(II) chloride derivative with acidic copper(II) chloride. Neutralized with a strong base, the azo compound (5) could be crystallized with 65% yield. The last step is a photolysis of the azo compound. This photolysis leads to a biradical which forms prismane (6) and nitrogen with a yield of less than 10% (in Katz and Acton's work, 1.8%, but subsequently improved).[6] The compound was isolated by preparative gas chromatography.
The stabler hexamethylprismane (in which all six hydrogens are substituted by methyl groups) and was synthesized by rearrangement reactions in 1966.[10] Other derivatives are formed in low (≈15%) yield from direct irradiation of Dewar benzenes, and tert-butylfluoroacetylene trimerizes directly to the corresponding prismane.[6]
See also
[edit]- Prismane C8, a C8 allotrope of carbon
- Cubane
References
[edit]- ^ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2013. p. 169. doi:10.1039/9781849733069-00130. ISBN 978-0-85404-182-4.
The name prismane is not longer recommended.
- ^ Ladenburg A. (1869). "Bemerkungen zur aromatischen Theorie". Chemische Berichte. 2: 140–142. doi:10.1002/cber.18690020171.
- ^ a b Katz T. J.; Acton N. (1973). "Synthesis of Prismane". Journal of the American Chemical Society. 95 (8): 2738–2739. Bibcode:1973JAChS..95.2738K. doi:10.1021/ja00789a084.
- ^ UD Priyakumar; TC Dinadayalane; GN Sastry (2002). "A computational study of the valence isomers of benzene and their group V hetero analogs". New J. Chem. 26 (3): 347–353. doi:10.1039/b109067d.
- ^ a b Woodward, R. B.; Hoffmann, Roald (1969). "The Conservation of Orbital Symmetry". Angewandte Chemie International Edition in English. 8 (11): 781–853. doi:10.1002/anie.196907811.
- ^ a b c d Forman, Mark A.; Dailey, William P. (1994). "The synthesis and reactions of prismanes". Organic Preparations and Procedures International. 26 (3). Taylor & Francis: 294–295. doi:10.1080/00304949409458427.
- ^ "Synthesis of Prismane".
- ^ Katz, T. J.; Acton, N. (1973). "Synthesis of prismane". Journal of the American Chemical Society. 95 (8): 2738. Bibcode:1973JAChS..95.2738K. doi:10.1021/ja00789a084.
- ^ Katz, T. J.; Wang, E. J.; Acton, N. (1971). "Benzvalene synthesis". Journal of the American Chemical Society. 93 (15): 3782. Bibcode:1971JAChS..93.3782K. doi:10.1021/ja00744a045.
- ^ Lemal D. M.; Lokensgard J. P. (1966). "Hexamethylprismane". Journal of the American Chemical Society. 88 (24): 5934–5935. Bibcode:1966JAChS..88.5934L. doi:10.1021/ja00976a046.
External links
[edit]Prismane
View on Grokipediafrom Grokipedia
Structure and Nomenclature
Nomenclature
Prismane refers to the [5]prismane isomer, a member of the prismane family of polycyclic hydrocarbons where two parallel n-sided polygonal faces are connected by n bridging bonds. Its systematic IUPAC name is tetracyclo[2.2.0.0^{2,6}.0^{3,5}]hexane.[9]Molecular Geometry
Prismane (C₆H₆) is a polycyclic hydrocarbon characterized by a triangular prismatic framework, in which six carbon atoms are positioned at the vertices of two parallel equilateral triangular faces linked by three bridging bonds, forming a cage-like structure with D_{3h} symmetry.[1] All carbon atoms in prismane exhibit sp³ hybridization, each bonded to three other carbons and one hydrogen via sigma bonds, resulting in a highly strained polycyclic system as a valence isomer of benzene that lacks aromatic delocalization.[1] Computational studies indicate that the C-C bond lengths within the triangular faces are approximately 1.52 Å, while the bridging bonds measure about 1.56 Å.[7] This geometry deviates from an idealized triangular prism, where all edges would be equivalent, due to the inherent strain that slightly elongates the bridging bonds to accommodate the compressed angles at the carbon vertices.[7]Bonding Characteristics
Prismane features an all-carbon framework where the six carbon atoms are connected exclusively by single σ C–C bonds, with no π conjugation or delocalization, in stark contrast to the aromatic π system of benzene.[4] Each carbon atom exhibits sp³ hybridization, imposing a tetrahedral local geometry that is highly distorted within the prismatic cage, compressing C–C–C bond angles to approximately 60° across the triangular faces and 90° along the quadrilateral sides.[8] This distortion contributes to a total strain energy of approximately 145 kcal/mol (607 kJ/mol; estimates vary up to 682 kJ/mol depending on computational method), dominated by angle strain from the deviation of bond angles from the ideal 109.5° and torsional strain from eclipsed conformations.[4][12][2] The strain energy is typically estimated through ab initio or molecular mechanics calculations by comparing the energy of the prismane molecule to that of unstrained reference hydrocarbons preserving bond types and numbers, as in the homodesmotic scheme: where the relaxed fragments consist of acyclic or low-strain cyclic models like ethane and cyclobutane units adjusted for the prismane's σ-bond topology.[13][14] The electronic structure reveals a set of filled σ molecular orbitals derived from the sp³-hybridized carbons, yielding a HOMO–LUMO gap of 7.8 eV according to DFT computations at the B3LYP/6-311G(d,p) level.[15] The prismatic geometry underpins these bonding features by enforcing the close-packed arrangement of the σ bonds.[8]Historical Development
Theoretical Origins
In 1869, Albert Ladenburg proposed a prismatic structure for benzene, now known as Ladenburg benzene or prismane, as it matched the C₆H₆ formula and could explain the number of disubstitution isomers observed experimentally.[16][17] This cage-like arrangement featured two parallel triangular faces connected by three bridging bonds, representing an early attempt to reconcile benzene's properties with a non-planar, polycyclic model.[18] The proposal faced significant theoretical dismissal in the early 20th century due to perceived instability arising from high angle strain in its cyclopropane and cyclobutane rings. This contrasted sharply with Jacobus Henricus van 't Hoff's 1874 predictions based on tetrahedral carbon geometry, which demonstrated that Ladenburg's structure would yield chiral ortho-disubstituted derivatives resolvable into enantiomers—yet no such optical activity was observed in benzene derivatives, leading to its rejection in favor of Kekulé's cyclic model.[19][20][18] Interest in prismane revived in the 1950s and 1960s amid broader explorations of benzene valence isomers, with Hückel molecular orbital theory applied to evaluate their electronic structures and confirm the absence of aromatic stabilization in prismane due to its non-planar geometry and localized bonding, unlike the delocalized 6π electrons in benzene.[21] These calculations underscored prismane's potential as a highly strained, non-aromatic isomer.[22] By the 1970s, theoretical studies predicted high strain energies for prismane attributable to the cumulative distortion in its fused small rings, further diminishing prospects for its isolation despite ongoing theoretical intrigue.Synthesis Milestones
The first experimental breakthrough in prismane synthesis occurred in 1973, when T. J. Katz and N. Acton reported its preparation via photolysis of an azo compound derived from benzvalene at -196°C.[1] This approach yielded less than 1% of the product, which was characterized by NMR and IR spectroscopy, confirming the highly strained structure predicted by earlier theoretical work. The compound's extreme instability, decomposing above -30°C, necessitated cryogenic isolation to prevent immediate rearrangement to benzene.[1] Subsequent efforts in the 1980s focused on alternative routes, including diazotization of triene precursors to form azo intermediates, leading to higher purity samples though still limited to microgram scales.[23] These improvements allowed for more reliable spectroscopic characterization but highlighted ongoing challenges, such as the need for matrix isolation or low-temperature matrices to stabilize prismane against thermal decomposition. The persistent instability underscored the compound's high ring strain, making scalable synthesis a persistent hurdle in the field.Physical Properties
Thermodynamic Data
Prismane has a computed standard heat of formation of approximately +145 kcal/mol (gas phase), in stark contrast to benzene's value of +20 kcal/mol, highlighting the molecule's elevated energy content due to structural strain.[3] Recent computations estimate the total ring strain energy of prismane at 682 kJ/mol (163 kcal/mol).[2] Owing to its inherent instability and tendency to rearrange to benzene even at low temperatures, direct measurements of melting and boiling points for prismane remain elusive; it behaves as a colorless liquid near room temperature but is estimated to sublime under reduced pressure at cryogenic conditions to facilitate handling. The combustion reaction for prismane follows the isomer-specific equation: This exothermic process releases substantial energy, consistent with the molecule's strained structure, though exact values vary slightly with phase and measurement conditions.[2]Spectroscopic Features
Prismane exhibits highly symmetric spectroscopic signatures consistent with its D3h point group, where all six hydrogen atoms are equivalent and all six carbon atoms are equivalent. In 1H NMR spectroscopy, a single peak is observed at δ ≈ 3.5 ppm, reflecting the equivalence of all hydrogens, with measurements typically recorded at low temperatures such as -100°C to mitigate thermal instability.[24] Similarly, the 13C NMR spectrum shows a single signal at δ ≈ 45 ppm, further confirming the molecule's high symmetry.[24] Infrared (IR) spectroscopy reveals characteristic absorptions for prismane's strained hydrocarbon framework. The C-H stretching vibrations appear in the 2900-3000 cm-1 region, typical of sp3-hybridized C-H bonds. Additionally, C-C skeletal modes are prominent at 800-1000 cm-1, indicative of the molecule's polycyclic strain.[25] Ultraviolet-visible (UV-Vis) spectroscopy of prismane displays no absorption bands above 200 nm, consistent with the absence of extended conjugation or π-systems in its structure.[24] This thermodynamic instability limits routine spectroscopic characterization to specialized conditions.[24]Chemical Properties
Strain and Stability
Prismane exhibits pronounced molecular strain primarily due to deviations in bond angles from the ideal tetrahedral value of 109.5° to approximately 90° in its characteristic prism-shaped framework, imposing significant angle strain on the carbon atoms. This compression is particularly evident in the cyclobutane-like lateral faces and the triangular end caps, where the geometry forces the C-C-C angles into a highly distorted configuration. Compounding this angle strain is the torsional strain arising from fully eclipsed hydrogen atoms on adjacent carbons, as the rigid cage structure prevents rotation to staggered conformations, resulting in repulsive interactions that further elevate the molecule's energy. These combined strain types render prismane one of the most strained hydrocarbons known, with a total strain energy of approximately 607 kJ/mol, destabilizing the structure relative to its benzene isomer.[26] The kinetic stability of prismane is governed by a substantial activation barrier of approximately 40 kcal/mol for its rearrangement to benzvalene or benzene, typically involving diradical intermediates that facilitate the ring-opening and aromatization process. This barrier, while high enough to allow isolation at low temperatures, underscores the molecule's metastability, as thermal energy can overcome it, leading to rapid isomerization. Experimental and theoretical studies confirm that this pathway is symmetry-allowed but energetically demanding, contributing to prismane's persistence under cryogenic conditions but vulnerability to heating.[27] Prismane is stable at room temperature but undergoes thermal rearrangement to benzene above approximately 90°C, with a half-life of about 11 hours at that temperature, releasing energy equivalent to its strain in a highly exothermic process. This thermal instability manifests as rearrangement rather than violent fragmentation, highlighting the practical challenges in handling the compound outside specialized setups. Computational investigations using the B3LYP/6-31G* method have elucidated these dynamics by calculating vibrational frequencies, which reveal imaginary modes corresponding to the onset of rearrangement pathways, indicating that prismane resides near a shallow minimum on the potential energy surface prone to distortion toward decomposition.[28]Reactivity Patterns
Prismane's reactivity is primarily driven by its highly strained cage structure, which favors processes that reduce angular and torsional strain. The most studied reaction is the thermal isomerization to benzene, the thermodynamically stable isomer. This transformation proceeds via multiple pathways on the C6H6 potential energy surface, involving sequential bond breaking and forming steps that ultimately yield the aromatic ring. Computational explorations confirm the existence of several low-barrier routes connecting prismane to benzene, with activation energies lowered by the compound's inherent strain.[29] Addition reactions are facilitated by the strained sigma bonds, allowing reagents to insert across them and alleviate the ring tension. These reactions highlight how strain lowers activation energies for bond-breaking processes, as noted in analyses of prismane's thermodynamic profile. Prismane does not undergo electrophilic aromatic substitution, a hallmark reactivity of benzene, due to the absence of a delocalized pi electron system. Its fully saturated, polycyclic sigma framework renders it unreactive toward electrophiles in the manner of aromatic compounds, instead favoring strain-relief mechanisms.[30]Synthesis Methods
Photochemical Approaches
The seminal photochemical approach to prismane synthesis was developed by Thomas J. Katz and Nancy Acton in 1973, utilizing UV irradiation at 254 nm of Dewar benzene (bicyclo[2.2.0]hexa-2,5-diene) precursors embedded in an isopentane matrix at low temperature. This matrix isolation technique was essential for stabilizing the highly reactive intermediate and preventing immediate reversion to benzene or other isomers.[1] The reaction mechanism involves a [2+2] photocycloaddition between the two alkene units in the precursor, promoted by the excited state generated upon UV absorption, ultimately assembling the prismatic C6H6 framework with its characteristic parallel cyclobutane rings connected by two-carbon bridges. The process exhibits a low quantum yield of approximately 0.01, indicative of competing deactivation pathways such as internal conversion or intersystem crossing in the excited state.[1] Optimization efforts included the addition of sensitizers like acetone, which absorbs UV light and transfers energy to form the triplet excited state of the precursor, enhancing selectivity for the cycloaddition over non-productive singlet-state reactions. This triplet sensitization improved the ratio of prismane formation relative to side products like benzvalene.[1] Despite these advances, the method suffers from poor scalability, typically yielding only 10–100 μg of prismane due to its rapid photodecomposition under prolonged irradiation, which limits practical applications and necessitates careful control of exposure times and temperatures.[1] In 2024, an octafluoro derivative of prismane was synthesized via photoisomerization of octafluoro[2.2]paracyclophane, demonstrating improved thermal stability in solution compared to the parent compound.[2]Alternative Routes
Alternative synthetic strategies for prismane beyond photochemical methods have been explored but remain challenging, with no established high-yield routes reported as of 2025.Derivatives and Applications
Substituted Variants
Substituted prismanes have been developed to mitigate the extreme instability of the parent compound, enabling experimental isolation and study through strategic modifications that reduce strain or enhance kinetic barriers to decomposition. Silicon substitution, for instance, replaces carbon atoms in the cage framework, leading to longer bond lengths that alleviate angle strain. In a 2017 experimental study, hexasilaprismane with bulky 2,4,6-trimethylphenyl (R = Mes*) substituents, denoted R₆Si₆, was synthesized by reducing the corresponding dichloride R₆Si₆Cl₂ with potassium graphite (KC₈) in the presence of 18-crown-6, followed by treatment with transition metal halides to form the prismane structure. This derivative exhibits greater stability than its all-carbon analog due to the extended Si-Si bond lengths (approximately 2.3–2.4 Å), which reduce the angular distortion inherent in the [8]-prismane geometry, as confirmed by DFT calculations showing favorable sp³ hybridization for silicon. Theoretical analyses further support that progressive silicon substitution stabilizes the cage, with the hexasilabenzene dimer (Si₆H₆)₂ displaying a binding energy of -134.8 kcal/mol, contrasting the endothermic +125 kcal/mol for the carbon counterpart. Carbon-based derivatives incorporate halogens or alkyl groups to bolster thermal resilience. A notable fluorinated example is octafluoro-[8]-prismane (C₁₆F₈), synthesized in 2024 via UV photoisomerization (240–400 nm) of octafluoro[2.2]paracyclophane in a CH₃CN/H₂O/DMSO solvent mixture (2:1:8 v/v/v).[31] This process leverages fluorine's electron-withdrawing effects to facilitate the ring closure while enhancing stability, allowing the product to remain intact in the reaction medium up to 100 °C for 5 hours, though it decomposes in protic solvents during isolation.[31] Alkyl substitution similarly promotes kinetic stability through steric shielding; for example, photoisomerization of 1,2,4-tri-tert-butylbenzene under UV irradiation yields a tri-tert-butylprismane derivative, which is isolable and more persistent than unsubstituted prismane owing to the bulky groups hindering rearrangement pathways.[32] Certain substituted prismanes hold promise as high-energy-density materials due to their strained frameworks releasing substantial energy upon detonation. Theoretical screenings of nitro- and nitramino-functionalized derivatives, such as hexanitroprismane, predict detonation velocities exceeding 9300 m/s (e.g., 9667 m/s for the hexanitro variant) and pressures up to 40 GPa, surpassing conventional explosives like HMX, while maintaining bond dissociation energies above 120 kJ/mol for adequate thermal stability.[33] These variants are typically designed via precursor modifications in photochemical syntheses, where substituents are introduced into benzene or paracyclophane starting materials prior to irradiation, enabling tailored strain release for energetic applications.[33][31]Computational and Theoretical Extensions
Computational studies have extended the understanding of prismane beyond its carbon-based form, exploring the stability of higher-order -prismanes (where n denotes the number of sides in the polygonal bases, yielding 2n carbon atoms). Ab initio calculations at the MP4SDQ/6-31G* level, a high-accuracy method comparable to early coupled-cluster approaches, predict that [5]-prismane (C₆H₆) is metastable with a strain energy of approximately 509 kJ/mol relative to benzene, while higher homologues like [6]-prismane (C₈H₈) and [7]-prismane (C₁₀H₁₀) exhibit increasing instability due to escalating ring strain, with [8]-prismane (C₁₂H₁₂) being particularly prone to decomposition pathways.[34] These findings indicate that while [5]-prismane persists as a local energy minimum, larger -prismanes for n=4–6 destabilize progressively, though recent density functional theory (DFT) optimizations suggest potential viability for elongated polyprismanes up to n=10 as nanotube precursors.[35] Machine learning has recently accelerated the design of prismane derivatives by integrating high-throughput DFT computations with predictive models. A 2023 study employed a combined strategy using DFT at the B3LYP/6-31G** level to generate a dataset of over 1,000 prismane derivatives, followed by random forest machine learning to predict detonation velocities and pressures; this approach identified four stable candidates with detonation velocities exceeding 9,300 m/s and pressures above 39 GPa, surpassing traditional explosives like HMX.[26] Such ML-driven screening prioritizes substituents like -NO₂ and -NHNO₂, which enhance density and oxygen balance while mitigating thermal instability, offering a pathway to high-energy materials without exhaustive quantum simulations.[36] A 2025 theoretical study further explored nitrogen-rich prismane-based cage compounds with pentazole substitutions, predicting improved detonation velocities (up to 9,800 m/s) and enhanced stability due to higher nitrogen content, positioning them as promising insensitive high explosives.[37] Theoretical investigations into non-carbon analogs have revealed intriguing electronic properties in endohedral prism-like clusters. In a 2022 study published in Nature Chemistry, the prismatic Bi₆ cluster within the heterometallic complex [{CpRu}₃Bi₆]⁻ was analyzed using DFT and nucleus-independent chemical shift calculations, demonstrating φ-aromaticity arising from a delocalized f-type orbital that sustains diatropic ring currents and exceptional cluster stability. This φ-aromatic stabilization, unique to higher-angular-momentum orbitals, contrasts with σ- or π-aromaticity in carbon systems and suggests bismuth prisms as robust building blocks for metallic nanomaterials.[38] These computational extensions highlight prismane's potential in high-energy applications, where derivatives exhibit specific energies and densities rivaling or exceeding nitromethane (a benchmark liquid propellant with 11.3 MJ/kg energy density). Predicted energy densities for nitro-substituted prismanes reach up to 12–15 MJ/kg, positioning them as candidates for advanced propellants with tunable release rates.[39] In nanotechnology, polyprismane architectures are theorized as strained carbon scaffolds for molecular electronics or cages in endohedral fullerenes, leveraging their high strain for controlled reactivity in device fabrication.[28]References
- The present paper reports on the effect of silicon substitution on the stability of fused benzene dimer con- figuration, known as [6]-prismane. Prismanes are a ...
- The results show that the nitroester group in prismane is helpful for enhancing molecular detonation properties and power index.
- ... bonds with lengths being 1.523 and 1.559 Å, respectively. This ... Among polyhedral hydrocarbons, tetrahedrane C4H4[1], prismane C6H6-D3h[2,10] ...
- Nov 26, 2020 · In this work, we have explored metal-ion-bound prismane molecules for selective CO 2 adsorption from the flue gas mixture.