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Foiled Carbene
A foiled carbene in organic chemistry is a special type of stabilized carbene due to the proximity of a double bond. This type of reactive intermediate is implicated in certain organic reactions. The positive interaction between carbene and double bond is only present in the singlet type and based on through-space electron transfer between the empty carbene p-orbital (LUMO) and filled alkene double bond p-orbitals (HOMO). The result is a three-center two-electron bond akin to certain non-classical ions. The increased stabilization blocks certain otherwise ordinary reaction modes for the carbene, hence the term ''foiled''. An example is ''norbornen-7-ylidene'', which is norbornene with a carbenic carbon atom at the bridge position. In silico experiments reveal that the bridge in this molecule is actually bending towards the double bond with an optimum angle of around 90° vs 130° for norbornene.''Foiled Carbenes Revisited: When -Stabilization Surpasses -Stabilization'' Jean-Luc M ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organic Chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; Greeves, N. and Warren, S. (2012) ''Organic Chemistry''. Oxford University Press. pp. 1–15. . Study of structure determines their structural formula. Study of properties includes physical and chemical properties, and evaluation of chemical reactivity to understand their behavior. The study of organic reactions includes the chemical synthesis of natural products, drugs, and polymers, and study of individual organic molecules in the laboratory and via theoretical ( in silico) study. The range of chemicals studied in organic chemistry includes hydrocarbons (compounds containing only carbon and hydrogen) as well as compounds based on carbon, but also containing other elements, especially oxygen, nitrogen, sulfur, phosphorus (included in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Carbene
In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is or where the R represents substituents or hydrogen atoms. The term "carbene" may also refer to the specific compound , also called methylene, the parent hydride from which all other carbene compounds are formally derived. Carbenes are classified as either singlets or triplets, depending upon their electronic structure. Most carbenes are very short lived, although persistent carbenes are known. One well-studied carbene is dichlorocarbene , which can be generated ''in situ'' from chloroform and a strong base. Structures and bonding The two classes of carbenes are singlet and triplet carbenes. Singlet carbenes are spin-paired. In the language of valence bond theory, the molecule adopts an sp2 hybrid structure. Triplet carbenes have two unpaired electrons. Most carbenes have a nonlinear triplet ground state, e ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Double Bond
In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist between two different elements: for example, in a carbonyl group between a carbon atom and an oxygen atom. Other common double bonds are found in azo compounds (N=N), imines (C=N), and sulfoxides (S=O). In a skeletal formula, a double bond is drawn as two parallel lines (=) between the two connected atoms; typographically, the equals sign is used for this. Double bonds were first introduced in chemical notation by Russian chemist Alexander Butlerov. Double bonds involving carbon are stronger and shorter than single bonds. The bond order is two. Double bonds are also electron-rich, which makes them potentially more reactive in the presence of a strong electron acceptor (as in addition reactions of the halogens). File:Ethene structural.svg ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Reactive Intermediate
In chemistry, a reactive intermediate or an intermediate is a short-lived, high-energy, highly reactive molecule. When generated in a chemical reaction, it will quickly convert into a more stable molecule. Only in exceptional cases can these compounds be isolated and stored, e.g. low temperatures, matrix isolation. When their existence is indicated, reactive intermediates can help explain how a chemical reaction takes place. Most chemical reactions take more than one elementary step to complete, and a reactive intermediate is a high-energy, yet stable, product that exists only in one of the intermediate steps. The series of steps together make a reaction mechanism. A reactive intermediate differs from a reactant or product or a simple reaction intermediate only in that it cannot usually be isolated but is sometimes observable only through fast spectroscopic methods. It is stable in the sense that an elementary reaction forms the reactive intermediate and the elementary reaction ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organic Reaction
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, Mechanistic Organic Photochemistry, photochemical reactions and organic redox reaction, redox reactions. In organic synthesis, organic reactions are used in the construction of new organic molecules. The production of many man-made chemicals such as drugs, plastics, food additives, fabrics depend on organic reactions. The oldest organic reactions are combustion of organic fuels and saponification of fats to make soap. Modern organic chemistry starts with the Wöhler synthesis in 1828. In the history of the Nobel Prize in Chemistry awards have been given for the invention of specific organic reactions such as the Grignard reaction in 1912, the Diels-Alder reaction in 1950, the Wittig reaction in 1979 and olefin metathesis in 2005. Classifications Organic c ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
P-orbital
In atomic theory and quantum mechanics, an atomic orbital is a Function (mathematics), function describing the location and wave-like behavior of an electron in an atom. This function can be used to calculate the probability of finding any electron of an atom in any specific region around the Atomic nucleus, atom's nucleus. The term ''atomic orbital'' may also refer to the physical region or space where the electron can be calculated to be present, as predicted by the particular mathematical form of the orbital. Each orbital in an atom is characterized by a set of values of the three quantum numbers , , and , which respectively correspond to the electron's energy, angular momentum, and an angular momentum vector component (magnetic quantum number). Alternative to the magnetic quantum number, the orbitals are often labeled by the associated Spherical harmonics#Harmonic polynomial representation, harmonic polynomials (e.g., ''xy'', ). Each such orbital can be occupied by a maximum o ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
LUMO
In chemistry, HOMO and LUMO are types of molecular orbitals. The acronyms stand for ''highest occupied molecular orbital'' and ''lowest unoccupied molecular orbital'', respectively. HOMO and LUMO are sometimes collectively called the ''frontier orbitals'', such as in the frontier molecular orbital theory. Gap The energy difference between the HOMO and LUMO is ''the HOMO–LUMO gap''. Its size can be used to predict the strength and stability of transition metal complexes, as well as the colors they produce in solution.Griffith, J. S. and L. E. Orgel"Ligand Field Theory" ''Q. Rev. Chem. Soc.'' 1957, 11, 381–383. As a rule of thumb, the larger a compound's HOMO-LUMO gap, the more stable the compound. Semiconductors The HOMO level is to organic semiconductors roughly what the maximum valence band is to inorganic semiconductors and quantum dots. The same analogy can be made between the LUMO level and the conduction band minimum.Bredas, J,-L"Mind the gap!" ''Mater. Horiz.'' 2 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
HOMO
''Homo'' () is the genus that emerged in the (otherwise extinct) genus ''Australopithecus'' that encompasses the extant species ''Homo sapiens'' ( modern humans), plus several extinct species classified as either ancestral to or closely related to modern humans (depending on the species), most notably ''Homo erectus'' and ''Homo neanderthalensis''. The genus emerged with the appearance of '' Homo habilis'' just over 2 million years ago. ''Homo'', together with the genus '' Paranthropus'', is probably sister to ''Australopithecus africanus'', which itself had previously split from the lineage of '' Pan'', the chimpanzees. ''Homo erectus'' appeared about 2 million years ago and, in several early migrations, spread throughout Africa (where it is dubbed ''Homo ergaster'') and Eurasia. It was likely that the first human species lived in a hunter-gatherer society and was able to control fire. An adaptive and successful species, ''Homo erectus'' persisted for more than a million ye ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Three-center Two-electron Bond
A three-center two-electron (3c–2e) bond is an electron-deficient chemical bond where three atoms share two electrons. The combination of three atomic orbitals form three molecular orbitals: one bonding, one ''non''-bonding, and one ''anti''-bonding. The two electrons go into the bonding orbital, resulting in a net bonding effect and constituting a chemical bond among all three atoms. In many common bonds of this type, the bonding orbital is shifted towards two of the three atoms instead of being spread equally among all three. Example molecules with 3c–2e bonds are the trihydrogen cation () and diborane (). In these two structures, the three atoms in each 3c-2e bond form an angular geometry, leading to a bent bond. Boranes and carboranes An extended version of the 3c–2e bond model features heavily in cluster compounds described by the polyhedral skeletal electron pair theory, such as boranes and carboranes. These molecules derive their stability from having a completel ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Non-classical Ion
Nonclassical carbocations are stabilized by charge delocalization from contributions of neighbouring or bonds, which can form bridged intermediates or transition states. Nonclassical ions have been extensively studied with the 2-norbornyl system, which as “naked” ion unambiguously exhibit such a bridged structure. The landmark of nonclassical ions are unexpectedly fast solvolysis rates and large differences between epimeric esters. Such behaviour is not restricted to 2-norbornyl esters, as has been shown with some cyclopentyl and steroidal esters with the tosyloxy leaving group. Substitution reactions of secondary esters occur by SN2- or SN1-like mechanisms. Only in highly polar solvents such as hexafluoroisopropanol (HFIP) of low nucleophilicity one can expect a nearly same uniform SN1-like mechanism. The solvolysis of several cyclopentyl and steroidal esters show that large solvolysis rates and differences between epimers can occur which surpass those of the 2-n ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
