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The plot of the Hammett equation is typically seen as being linear, with either a positive or negative slope correlating to the value of rho. However, nonlinearity emerges in the Hammett plot when a substituent affects the rate of reaction or changes the rate-determining step or reaction mechanism of the reaction. For the reason of the former ...
Transmetalation (alt. spelling: transmetallation) is a type of organometallic reaction that involves the transfer of ligands from one metal to another. It has the general form: M 1 –R + M 2 –R′ → M 1 –R′ + M 2 –R
Subsequently, the second partner undergoes transmetallation with a source of R' −. The final step is reductive elimination of the two coupling fragments to regenerate the catalyst and give the organic product. Unsaturated substrates, such as C(sp)−X and C(sp 2)−X bonds, couple more easily, in part because they add readily to the catalyst.
The Hammett equation predicts the equilibrium constant or reaction rate of a reaction from a substituent constant and a reaction type constant. The Edwards equation relates the nucleophilic power to polarisability and basicity. The Marcus equation is an example of a quadratic free-energy relationship (QFER). [citation needed]
The Curtin–Hammett principle is a principle in chemical kinetics proposed by David Yarrow Curtin and Louis Plack Hammett.It states that, for a reaction that has a pair of reactive intermediates or reactants that interconvert rapidly (as is usually the case for conformational isomers), each going irreversibly to a different product, the product ratio will depend both on the difference in ...
Louis Plack Hammett (April 7, 1894 – February 9, 1987) was an American physical chemist. He is known for the Hammett equation , which relates reaction rates to equilibrium constants for certain classes of organic reactions involving substituted aromatic compounds.
Hammett defined the equation based on two parameters: the reaction constant (ρ) and the substituent parameter (σ). When other reactions were studied using these parameters, a correlation was not always found due to the specific derivation of these parameters from the dissociation equilibrium of substituted benzoic acids and the original ...
The [2,3]-Wittig rearrangement is the transformation of an allylic ether into a homoallylic alcohol via a concerted, pericyclic process.Because the reaction is concerted, it exhibits a high degree of stereocontrol, and can be employed early in a synthetic route to establish stereochemistry.