- Settore: Chemistry
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The International Union of Pure and Applied Chemistry (IUPAC) serves to advance the worldwide aspects of the chemical sciences and to contribute to the application of chemistry in the service of people and the environment. As a scientific, international, non-governmental and objective body, IUPAC ...
(1) In quantum mechanics: A state that does not evolve with time.
(2) In kinetics: See steady state.
Industry:Chemistry
A chemical reaction with at least one reaction intermediate and involving at least two consecutive elementary reactions.
Industry:Chemistry
Pertaining to the dependence of the properties (especially the energy) of a molecular entity in a particular electronic state (or of a transition state) on relative nuclear geometry. The electronic ground state is usually considered, but the term can apply to excited states as well. Stereoelectronic effects are ascribed to the different alignment of electronic orbitals in different arrangements of nuclear geometry.
Industry:Chemistry
Control of the nature of the products of a chemical reaction (or of its rate) by stereoelectronic factors. The term is usually applied in the framework of an orbital approximation. The variations of molecular orbital energies with relative nuclear geometry (along a reaction coordinate) are then seen as consequences of variations in basis-orbital overlaps.
Industry:Chemistry
Stereoselectivity is the preferential formation in a chemical reaction of one stereoisomer over another. When the stereoisomers are enantiomers, the phenomenon is called enantioselectivity and is quantitatively expressed by the enantiomer excess; when they are diastereoisomers, it is called diastereoselectivity and is quantitatively expressed by the diastereomer excess. Reactions are termed (100%) stereoselective if the discrimination is complete or partially (x%) stereoselective if one product predominates. The discrimination may also be referred to semiquantitatively as high or low stereoselectivity.
Industry:Chemistry
(1) A reaction is termed stereospecific if starting materials differing only in their configuration are converted into stereoisomeric products. According to this definition, a stereospecific process is necessarily stereoselective but not all stereoselective processes are stereospecific. Stereospecificity may be total (100%) or partial. The term is also applied to situations where reaction can be performed with only one stereoisomer. For example the exclusive formation of trans-1,2-dibromocyclohexane upon bromination of cyclohexene is a stereospecific process, although the analogous reaction with (E)-cyclohexene has not been performed.
(2) The term has also been applied to describe a reaction of very high stereoselectivity, but this usage is unnecessary and is discouraged.
Industry:Chemistry
(1) A reaction is termed stereospecific if starting materials differing only in their configuration are converted into stereoisomeric products. According to this definition, a stereospecific process is necessarily stereoselective but not all stereoselective processes are stereospecific. Stereospecificity may be total (100%) or partial. The term is also applied to situations where reaction can be performed with only one stereoisomer. For example the exclusive formation of trans-1,2-dibromocyclohexane upon bromination of cyclohexene is a stereospecific process, although the analogous reaction with (E)-cyclohexene has not been performed.
(2) The term has also been applied to describe a reaction of very high stereoselectivity, but this usage is unnecessary and is discouraged.
Industry:Chemistry
The effect on a chemical or physical property (structure, rate or equilibrium constant) upon introduction of substituents having different steric requirements. The steric effect in a reaction is ascribed to the difference in steric energy between, on the one hand, reactants and, on the other hand, a transition state, (or products). A steric effect on a rate process may result in a rate increase ("steric acceleration") or a decrease ("steric retardation"). (The adjective "steric" is not to be confused with stereochemical.)
Steric effects arise from contributions ascribed to strain as the sum of (1) non-bonded repulsions, (2) bond angle strain, and (3) bond stretches or compressions.
For the purpose of correlation analysis or linear free-energy relations various scales of steric parameters have been proposed, notably A values, Taft's E<sub>s</sub> and Charton's υ scales.
In a reactant molecule RY and an appropriate reference molecule R<sup>0</sup>Y, the "primary steric effect" of R is the direct result of differences in compressions which occur because R differs from R<sup>0</sup> in the vicinity of the reaction center Y. A "secondary steric effect" involves the differential moderation of electron delocalization by non-bonded compressions.
Some authors make a distinction between "steric" effects attributed to van der Waals repulsions alone, and "strain" effects, attributed to deviations of bond angles from "ideal" values. CHARTON (1987). See Taft equation, van der Waals forces.
Industry:Chemistry
The original term for a steric effect arising from crowding of substituents.
Industry:Chemistry
A secondary isotope effect attributed to the different vibrational amplitudes of isotopologues. For example, both the mean and mean-square amplitudes of vibrations associated with C-H bonds are greater than those of C-D bonds. The greater effective bulk of molecules containing the former may be manifested by a steric effect on a rate or equilibrium constant.
Industry:Chemistry
