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The Ritchie equation, derived in 1972, is another free-energy relationship: [6] [7] [8] = + where N + is the nucleophile dependent parameter and k 0 the reaction rate constant for water. In this equation, a substrate-dependent parameter like s in
The Edwards equation in organic chemistry is a two-parameter equation for correlating nucleophilic reactivity, as defined by relative rate constants, with the basicity of the nucleophile (relative to protons) and its polarizability. This equation was first developed by John O. Edwards in 1954 [1] and later revised based on additional work in ...
The nucleophile may be electrically neutral or negatively charged, whereas the substrate is typically neutral or positively charged. An example of nucleophilic substitution is the hydrolysis of an alkyl bromide, R-Br under basic conditions, where the attacking nucleophile is hydroxyl (OH −) and the leaving group is bromide (Br −).
In physical organic chemistry, the Grunwald–Winstein equation is a linear free energy relationship between relative rate constants and the ionizing power of various solvent systems, describing the effect of solvent as nucleophile on different substrates. The equation, which was developed by Ernest Grunwald and Saul Winstein in 1948, could be ...
If the nucleophile is a neutral molecule (i.e. a solvent) a third step is required to complete the reaction. When the solvent is water, the intermediate is an oxonium ion. This reaction step is fast. Deprotonation: Removal of a proton on the protonated nucleophile by water acting as a base forming the alcohol and a hydronium ion. This reaction ...
Nucleophile strength is also affected by charge and electronegativity: nucleophilicity increases with increasing negative charge and decreasing electronegativity. For example, OH − is a better nucleophile than water, and I − is a better nucleophile than Br − (in polar protic solvents). In a polar aprotic solvent, nucleophilicity increases ...
An application of HSAB theory is the so-called Kornblum's rule (after Nathan Kornblum) which states that in reactions with ambident nucleophiles (nucleophiles that can attack from two or more places), the more electronegative atom reacts when the reaction mechanism is S N 1 and the less electronegative one in a S N 2 reaction.
Another deviation from the regular Hammett equation is explained by the charge of nucleophile. [15] [non-primary source needed] Despite nonlinearity in benzylic SN2 reactions, electron withdrawing groups could either accelerate or retard the reaction. If the nucleophile is negatively charged (e.g. cyanide) the electron withdrawing group will ...