[n]Radialenes are alicyclic organic compounds containing n cross-conjugated exocyclic double bonds. [1] [2] [3] [4] The double bonds are commonly alkene groups but those with a carbonyl (C=O) group are also called radialenes. [5] For some members the unsubstituted parent radialenes are elusive but many substituted derivatives are known.
Radialenes are related to open-chain dendralenes and also to compounds like butadiene and benzene which also consist of a ring of sp2 hybridized carbon atoms.
Radialenes are investigated in organic chemistry for their unusual properties and reactivity but have not ventured outside the laboratory. Reported uses are as experimental building blocks for novel organic conductors and ferromagnets. [6] The first radialene called hexaethylidencyclohexane was synthesised in 1961. [7]
[3] and [4]radialenes are expected to have a planar molecular geometry with all carbon atoms in the same plane. This is verified experimentally in hexamethyl[3]radialene and cyclobutanetetraonetetrakis(hydrazone). Decamethyl[5]radialene has a twist envelope geometry with C2 symmetry while a chair conformation is calculated for [6]radialene and found experimentally for hexa-(ethylidene)cyclohexane
Due to their specific pi-electron distributions, hydrocarbons such as perylene and triphenylene are not considered radialenes. One study [6] describes a [6]radialene composed of thiophene units: [8]
This compound is reported as planar with D3h symmetry (X-ray diffraction) but not aromatic: the carbon-carbon bond lengths are unusually long (145 pm vs. 140 pm for benzene) and the calculated NICS value is close to zero.
The parent [3], [4], [5] and [6]radialenes polymerize when in contact with oxygen.
[3]Radialene or trimethylenecyclopropane was synthesised in 1965. [9] [10] [11] Reported derivatives are triquinocyclopropanes, [12] [13] [14] salts of trimethylenecyclopropane dianions, [15] tris(thioxanthen-9-ylidene)cyclopropane, [16] tris(fluoren-9-ylidene)cyclopropane [17] and hexakis(trimethylsilylethynyl)[3]radialene. [18] Phosphorus derivatives (based on 4,5,6-triphospha[3]radialene) have also been reported. [19] [20] [21] [22] Phospharadialenes have been investigated as quantum efficiency improvers in solar cells [23] Hexakis[4-(diarylamino)phenyl][3]radialene derivatives have been investigated for their low oxidation potentials. [24]
The unsubstituted [4]radialene has been prepared in an elimination reaction of cis,trans,cis-tetra(bromomethyl)cyclobutane with sodium methoxide in ethanol. [25]
Hydrogenation with platinum on carbon gives cis,cis,cis-tetramethylcyclobutane in accordance with the proposed structure.
Successful low-temperature synthesis of the parent compound [5]radialene was reported in 2015. [26]
The parent [6]radialene is unstable and polymerises immediately on formation. It has been synthesised from 1,5,9-cyclododecatriyne, 1,3,6-tri(chloromethyl)mesitylene and tricyclobutabenzene. [27] [28] [29] [30]
Only substituted [6]radialenes exist as stable compounds. Stable derivatives are the hexamethyl substituted, [7] [31] dodecamethyl substituted [32] and hexabromo substituted [33] radialene.
A trisalkoxy-substituted radialene has also been reported, [34] the central ring adopting a non-planar twist-boat conformation:
Radialenes have been researched as a potential way to access complex synthetic molecules [35] [36] and in polymer synthesis. [37] [38]
Tetrahedrane is a hypothetical platonic hydrocarbon with chemical formula C4H4 and a tetrahedral structure. The molecule would be subject to considerable angle strain and has not been synthesized as of 2021. However, a number of derivatives have been prepared. In a more general sense, the term tetrahedranes is used to describe a class of molecules and ions with related structure, e.g. white phosphorus.
Pentalene is a polycyclic hydrocarbon composed of two fused cyclopentadiene rings. It has chemical formula C8H6. It is antiaromatic, because it has 4n π electrons where n is any integer. For this reason it dimerizes even at temperatures as low as −100 °C. The derivative 1,3,5-tri-tert-butylpentalene was synthesized in 1973. Because of the tert-butyl substituents this compound is thermally stable. Pentalenes can also be stabilized by benzannulation for example in the compounds benzopentalene and dibenzopentalene.
The Simmons–Smith reaction is an organic cheletropic reaction involving an organozinc carbenoid that reacts with an alkene to form a cyclopropane. It is named after Howard Ensign Simmons, Jr. and Ronald D. Smith. It uses a methylene free radical intermediate that is delivered to both carbons of the alkene simultaneously, therefore the configuration of the double bond is preserved in the product and the reaction is stereospecific.
Grubbs catalysts are a series of transition metal carbene complexes used as catalysts for olefin metathesis. They are named after Robert H. Grubbs, the chemist who supervised their synthesis. Several generations of the catalyst have been developed. Grubbs catalysts tolerate many functional groups in the alkene substrates, are air-tolerant, and are compatible with a wide range of solvents. For these reasons, Grubbs catalysts have become popular in synthetic organic chemistry. Grubbs, together with Richard R. Schrock and Yves Chauvin, won the Nobel Prize in Chemistry in recognition of their contributions to the development of olefin metathesis.
A dendralene is a discrete acyclic cross-conjugated polyene. The simplest dendralene is buta-1,3-diene (1) or [2]dendralene followed by [3]dendralene (2), [4]dendralene (3) and [5]dendralene (4) and so forth. [2]dendralene (butadiene) is the only one not cross-conjugated.
In organic chemistry, a bent bond, also known as a banana bond, is a type of covalent chemical bond with a geometry somewhat reminiscent of a banana. The term itself is a general representation of electron density or configuration resembling a similar "bent" structure within small ring molecules, such as cyclopropane (C3H6) or as a representation of double or triple bonds within a compound that is an alternative to the sigma and pi bond model.
A persistent carbene (also known as stable carbene) is a type of carbene demonstrating particular stability. The best-known examples and by far largest subgroup are the N-heterocyclic carbenes (NHC) (sometimes called Arduengo carbenes), for example diaminocarbenes with the general formula (R2N)2C:, where the four R moieties are typically alkyl and aryl groups. The groups can be linked to give heterocyclic carbenes, such as those derived from imidazole, imidazoline, thiazole or triazole.
Homoaromaticity, in organic chemistry, refers to a special case of aromaticity in which conjugation is interrupted by a single sp3 hybridized carbon atom. Although this sp3 center disrupts the continuous overlap of p-orbitals, traditionally thought to be a requirement for aromaticity, considerable thermodynamic stability and many of the spectroscopic, magnetic, and chemical properties associated with aromatic compounds are still observed for such compounds. This formal discontinuity is apparently bridged by p-orbital overlap, maintaining a contiguous cycle of π electrons that is responsible for this preserved chemical stability.
A circulene is a macrocyclic arene in which a central polygon is surrounded and fused by benzenoids. Nomenclature within this class of molecules is based on the number of benzene rings surrounding the core, which is equivalent to the size of the central polygon. Examples which have been synthesized include [5]circulene (corannulene), [6]circulene (coronene), [7]circulene, and [12]circulene (kekulene) These compounds belong to a larger class of geodesic polyarenes. Whereas [5]circulene is bowl-shaped and [6]circulene is planar, [7]circulene has a unique saddle-shaped structure. The helicenes are a conceptually related class of structures in which the array of benzene rings form an open helix rather than a closed ring.
In organic chemistry, organocatalysis is a form of catalysis in which the rate of a chemical reaction is increased by an organic catalyst. This "organocatalyst" consists of carbon, hydrogen, sulfur and other nonmetal elements found in organic compounds. Because of their similarity in composition and description, they are often mistaken as a misnomer for enzymes due to their comparable effects on reaction rates and forms of catalysis involved.
The Wanzlick equilibrium is a chemical equilibrium between a relatively stable carbene compound and its dimer. The equilibrium was proposed to apply to certain electron-rich alkenes, such as tetraminoethylenes, which have been called "carbene dimers." Such equilibria occur, but the mechanism does not proceed simply, but requires catalysts.
The Kulinkovich reaction describes the organic synthesis of cyclopropanols via reaction of esters with dialkyldialkoxytitanium reagents, generated in situ from Grignard reagents bearing hydrogen in beta-position and titanium(IV) alkoxides such as titanium isopropoxide. This reaction was first reported by Oleg Kulinkovich and coworkers in 1989.
Group 2 organometallic chemistry refers to the chemistry of compounds containing carbon bonded to any group 2 element. By far the most common group 2 organometallic compounds are the magnesium-containing Grignard reagents which are widely used in organic chemistry. Other organmetallic group 2 compounds are rare and are typically limited to academic interests.
Spirotryprostatin B is an indolic alkaloid found in the Aspergillus fumigatus fungus that belongs to a class of naturally occurring 2,5-diketopiperazines. Spirotryprostatin B and several other indolic alkaloids have been found to have anti-mitotic properties, and as such they have become of great interest as anti-cancer drugs. Because of this, the total syntheses of these compounds is a major pursuit of organic chemists, and a number of different syntheses have been published in the chemical literature.
Dihydroimidazol-2-ylidene is a hypothetical organic compound with formula C3H6N2. It would be a heterocyclic compound, formally derived from imidazolidine with two hydrogen atoms removed from carbon number 2, leaving two vacant chemical bonds — which makes it a carbene.
Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend to be more common.
Peter Michael Maitlis, FRS was a British organometallic chemist.
A silanone in chemistry is the silicon analogue of a ketone. The general description for this class of organic compounds is R1R2Si=O, with silicon connected to a terminal oxygen atom via a double bond and also with two organic residues (R). Silanones are extremely reactive and until 2013 were only detected by argon matrix isolation or in the gas phase but not isolated. A synthesis of a stable silanone was reported in 2014. Silanones are of some interest to academic research, with their reactivity being of some relevance to the double bond rule.
Michal Hocek is a Czech chemist. He is a group leader at the Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences and a professor of organic chemistry at Charles University in Prague. He specializes in the chemistry and chemical biology of nucleosides, nucleotides, and nucleic acids.
Abiological nitrogen fixation describes chemical processes that fix (react with) N2, usually with the goal of generating ammonia. The dominant technology for abiological nitrogen fixation is the Haber process, which uses an iron-based heterogeneous catalysts and H2 to convert N2 to NH3. This article focuses on homogeneous (soluble) catalysts for the same or similar conversions.