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Steric
Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivity of ions and molecules. Steric effects complement electronic effects, which dictate the shape and reactivity of molecules. Steric repulsive forces between overlapping electron clouds result in structured groupings of molecules stabilized by the way that opposites attract and like charges repel. Steric hindrance Steric hindrance is a consequence of steric effects. Steric hindrance is the slowing of chemical reactions due to steric bulk. It is usually manifested in ''intermolecular reactions'', whereas discussion of steric effects often focus on ''intramolecular interactions''. Steric hindrance is often exploited to control selectivity, such as slowing unwanted side-reactions. Steric hindrance between adjacent groups can also affect torsional ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Conformational Isomerism
In chemistry, conformational isomerism is a form of stereoisomerism in which the isomers can be interconverted just by rotations about formally single bonds (refer to figure on single bond rotation). While any two arrangements of atoms in a molecule that differ by rotation about single bonds can be referred to as different conformations, conformations that correspond to local minima on the potential energy surface are specifically called conformational isomers or conformers. Conformations that correspond to local maxima on the energy surface are the transition states between the local-minimum conformational isomers. Rotations about single bonds involve overcoming a rotational energy barrier to interconvert one conformer to another. If the energy barrier is low, there is free rotation and a sample of the compound exists as a rapidly equilibrating mixture of multiple conformers; if the energy barrier is high enough then there is restricted rotation, a molecule may exist for a r ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
A Value
400px, The A-value for a methyl group is 1.74 as derived from the chemical equilibrium above. This means it costs of energy to have a methyl group in the axial position compared to the equatorial position. A-values are numerical values used in the determination of the most stable orientation of atoms in a molecule (Conformational isomerism, conformational analysis), as well as a general representation of steric bulk. A-values are derived from energy measurements of the different cyclohexane conformations of a monosubstituted cyclohexane chemical. Substituents on a cyclohexane ring prefer to reside in the equatorial position to the axial. The difference in Gibbs free energy (ΔG) between the higher energy conformation (axial substitution) and the lower energy conformation (equatorial substitution) is the A-value for that particular substituent. Utility A-values help predict the conformation of cyclohexane rings. The most stable conformation will be the one which has the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electronic Effects
An electronic effect influences the structure, reactivity, or properties of molecule but is neither a traditional bond nor a steric effect. In organic chemistry, the term stereoelectronic effect is also used to emphasize the relation between the electronic structure and the geometry (stereochemistry) of a molecule. Types Induction is the redistribution of electron density through a traditional sigma bonded structure according to the electronegativity of the atoms involved. The inductive effect drops across every sigma bond involved limiting its effect to only a few bonds. Conjugation is a redistribution of electron density similar to induction but transmitted through interconnected pi-bonds. Conjugation is not only affected by electronegativity of the connected atoms but also affected by the position of electron lone pairs with respect to the pi-system. Electronic effects can be transmitted throughout a pi-system allowing their influence to extend further than induction. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ligand
In coordination chemistry, a ligand is an ion or molecule ( functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical areas, including bioinorganic and medicinal chemistry, homogeneous catalysis, and environment ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ligand Cone Angle
In coordination chemistry, the ligand cone angle (a common example being the Tolman cone angle or ''θ'') is a measure of the steric bulk of a ligand in a transition metal coordination complex. It is defined as the solid angle formed with the metal at the vertex and the outermost edge of the van der Waals spheres of the ligand atoms at the perimeter of the cone (see figure). Tertiary phosphine ligands are commonly classified using this parameter, but the method can be applied to any ligand. The term ''cone angle'' was first introduced by Chadwick A. Tolman, a research chemist at DuPont. Tolman originally developed the method for phosphine ligands in nickel complexes, determining them from measurements of accurate physical models. Asymmetric cases The concept of cone angle is most easily visualized with symmetrical ligands, e.g. PR3. But the approach has been refined to include less symmetrical ligands of the type PRR′R″ as well as diphosphines. In such asymmetric cases, the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ceiling Temperature
Ceiling temperature (T_c) is a measure of the tendency of a polymer to revert to its constituent monomers. When a polymer is at its ceiling temperature, the rate of polymerization and depolymerization of the polymer are equal. Generally, the ceiling temperature of a given polymer is correlated to the steric hindrance of the polymer’s monomers. Polymers with high ceiling temperatures are often commercially useful. Polymers with low ceiling temperatures are more readily depolymerizable. Thermodynamics of polymerization At constant temperature, the reversibility of polymerization can be determined using the Gibbs free energy equation: :\Delta G_p = \Delta H_p - T \Delta S_p where \Delta S_p is the change of entropy during polymerization. The change of enthalpy during polymerization, \Delta H_p, is also known as the heat of polymerization, which is defined by :\Delta H_p = E_p - E_ where E_p and E_ denote the activation energies for polymerization and depoly ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
1,3-butadiene
1,3-Butadiene () is the organic compound with the formula (CH2=CH)2. It is a colorless gas that is easily condensed to a liquid. It is important industrially as a precursor to synthetic rubber. The molecule can be viewed as the union of two vinyl groups. It is the simplest conjugated diene. Although butadiene breaks down quickly in the atmosphere, it is nevertheless found in ambient air in urban and suburban areas as a consequence of its constant emission from motor vehicles. The name butadiene can also refer to the isomer, 1,2-butadiene, which is a cumulated diene with structure H2C=C=CH−CH3. This allene has no industrial significance. History In 1863, the French chemist E. Caventou isolated butadiene from the pyrolysis of amyl alcohol. This hydrocarbon was identified as butadiene in 1886, after Henry Edward Armstrong isolated it from among the pyrolysis products of petroleum. In 1910, the Russian chemist Sergei Lebedev polymerized butadiene and obtained a material ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Biphenyl
Biphenyl (also known as diphenyl, phenylbenzene, 1,1′-biphenyl, lemonene or BP) is an organic compound that forms colorless crystals. Particularly in older literature, compounds containing the functional group consisting of biphenyl less one hydrogen (the site at which it is attached) may use the prefixes xenyl or diphenylyl. It has a distinctively pleasant smell. Biphenyl is an aromatic hydrocarbon with a molecular formula (C6H5)2. It is notable as a starting material for the production of polychlorinated biphenyls (PCBs), which were once widely used as dielectric fluids and heat transfer agents. Biphenyl is also an intermediate for the production of a host of other organic compounds such as emulsifiers, optical brighteners, crop protection products, and plastics. Biphenyl is insoluble in water, but soluble in typical organic solvents. The biphenyl molecule consists of two connected phenyl rings. Properties and occurrence Biphenyl occurs naturally in coal tar, crude oi ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tert-butyl
In organic chemistry, butyl is a four-carbon alkyl radical or substituent group with general chemical formula , derived from either of the two isomers (''n''-butane and isobutane) of butane. The isomer ''n''-butane can connect in two ways, giving rise to two "-butyl" groups: * If it connects at one of the two terminal carbon atoms, it is normal butyl or ''n''-butyl: (preferred IUPAC name: butyl) * If it connects at one of the non-terminal (internal) carbon atoms, it is secondary butyl or ''sec''-butyl: (preferred IUPAC name: butan-2-yl) The second isomer of butane, isobutane, can also connect in two ways, giving rise to two additional groups: * If it connects at one of the three terminal carbons, it is isobutyl: (preferred IUPAC name: 2-methylpropyl) * If it connects at the central carbon, it is tertiary butyl, ''tert''-butyl or ''t''-butyl: (preferred IUPAC name: ''tert''-butyl) Nomenclature According to IUPAC nomenclature, "isobutyl", "''sec''-butyl", and "''tert''-b ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Polymerization
In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many forms of polymerization and different systems exist to categorize them. In chemical compounds, polymerization can occur via a variety of reaction mechanisms that vary in complexity due to the functional groups present in the reactants and their inherent steric effects. In more straightforward polymerizations, alkenes form polymers through relatively simple radical reactions; in contrast, reactions involving substitution at a carbonyl group require more complex synthesis due to the way in which reactants polymerize. Alkanes can also be polymerized, but only with the help of strong acids. As alkenes can polymerize in somewhat straightforward radical reactions, they form useful compounds such as polyethylene and polyvinyl chloride (PVC ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Styrene
Styrene () is an organic compound with the chemical formula C6H5CH=CH2. This derivative of benzene is a colorless oily liquid, although aged samples can appear yellowish. The compound evaporates easily and has a sweet smell, although high concentrations have a less pleasant odor. Styrene is the precursor to polystyrene and several copolymers. Approximately 25 million tonnes of styrene were produced in 2010, increasing to around 35 million tonnes by 2018. Natural occurrence Styrene is named after storax balsam (often commercially sold as ''styrax''), the resin of Liquidambar trees of the Altingiaceae plant family. Styrene occurs naturally in small quantities in some plants and foods (cinnamon, coffee beans, balsam trees and peanuts) and is also found in coal tar. History In 1839, the German apothecary Eduard Simon isolated a volatile liquid from the resin (called ''storax'' or ''styrax'' (Latin)) of the American sweetgum tree (''Liquidambar styraciflua''). He called th ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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