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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.
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.
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 ...
Gas exchange is the physical process by which gases move passively by diffusion across a surface. For example, this surface might be the air/water interface of a water body, the surface of a gas bubble in a liquid, a gas-permeable membrane, or a biological membrane that forms the boundary between an organism and its extracellular environment.
These stabilities occur because of a partial overlap between the C–Si σ orbital and the σ* antibonding orbital at the β position, lowering the S N reaction transition state's energy. This hyperconjugation requires an antiperiplanar relationship between the Si group and the leaving group to maximize orbital overlap. [1]
The alpha effect refers to the increased nucleophilicity of an atom due to the presence of an adjacent (alpha) atom with lone pair electrons. [2] This first atom does not necessarily exhibit increased basicity compared with a similar atom without an adjacent electron-donating atom, resulting in a deviation from the classical Brønsted-type ...
Hydrogen–deuterium exchange (also called H–D or H/D exchange) is a chemical reaction in which a covalently bonded hydrogen atom is replaced by a deuterium atom, or vice versa. It can be applied most easily to exchangeable protons and deuterons, where such a transformation occurs in the presence of a suitable deuterium source, without any ...
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 ...