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Other researchers have found similar results or very different results. An alternative explanation for the effect is differential solvation as orders invert on going from the solution phase to the gas phase. [5] Today, the conjugation of neighbouring pi orbitals and polarised sigma bonds is known as hyperconjugation.
The exchange reaction can be followed using a variety of methods (see Detection). Since this exchange is an equilibrium reaction, the molar amount of deuterium should be high compared to the exchangeable protons of the substrate. For instance, deuterium is added to a protein in H 2 O by diluting the H 2 O solution with D 2 O (e.g. tenfold ...
Hyperconjugation can be used to rationalize a variety of chemical phenomena, including the anomeric effect, the gauche effect, the rotational barrier of ethane, the beta-silicon effect, the vibrational frequency of exocyclic carbonyl groups, and the relative stability of substituted carbocations and substituted carbon centred radicals, and the thermodynamic Zaitsev's rule for alkene stability.
A primary kinetic isotope effect (PKIE) may be found when a bond to the isotopically labeled atom is being formed or broken. [3] [4]: 427 Depending on the way a KIE is probed (parallel measurement of rates vs. intermolecular competition vs. intramolecular competition), the observation of a PKIE is indicative of breaking/forming a bond to the isotope at the rate-limiting step, or subsequent ...
The alpha effect is also dependent on solvent but not in a predictable way: it can increase or decrease with solvent mix composition or even go through a maximum. [12] At least in some cases, the alpha effect has been observed to vanish if the reaction is conducted in the gas phase, leading some to conclude that it is primarily a solvation ...
The other class is a cycle of reactions called the triple-alpha process, which consumes only helium, and produces carbon. [1] The alpha process most commonly occurs in massive stars and during supernovae. Both processes are preceded by hydrogen fusion, which produces the helium that fuels both the triple-alpha process and the alpha ladder ...
The Cieplak effect relies on the stabilizing interaction of mixing full and empty orbitals to delocalize electrons, known as hyperconjugation. [2] When the highest occupied molecular orbital of one system and the lowest unoccupied molecular orbital of another system have comparable energies and spatial overlap, the electrons can delocalize and sink into a lower energy level.
Negative hyperconjugation is seldom observed, though it can be most commonly observed when the σ *-orbital is located on certain C–F or C–O bonds. [ 3 ] [ 4 ] In negative hyperconjugation, the electron density flows in the opposite direction (from a π- or p-orbital to an empty σ * -orbital) than it does in the more common ...