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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 p-orbitals oriented in the z-direction (p z) can overlap end-on forming a bonding (symmetrical) σ orbital and an antibonding σ* molecular orbital. In contrast to the sigma 1s MO's, the σ 2p has some non-bonding electron density at either side of the nuclei and the σ* 2p has some electron density between the nuclei.
This lists the character tables for the more common molecular point groups used in the study of molecular symmetry. These tables are based on the group-theoretical treatment of the symmetry operations present in common molecules, and are useful in molecular spectroscopy and quantum chemistry. Information regarding the use of the tables, as well ...
The qualitative approach of MO analysis uses a molecular orbital diagram to visualize bonding interactions in a molecule. In this type of diagram, the molecular orbitals are represented by horizontal lines; the higher a line the higher the energy of the orbital, and degenerate orbitals are placed on the same level with a space between them.
The radical intermediate is stabilized by hyperconjugation. In the more substituted position, more carbon-hydrogen bonds are aligned with the radical's electron deficient molecular orbital. This means that there are greater hyperconjugation effects, so that position is more favorable. [5]
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.
In Figure 6, 2-chloro-2,3-dimethylbutane is stabilized through hyperconjugation from electron donation from σ C-H into σ* C-Cl, but both C–H and C–Cl bonds are weakened. A molecular orbital diagram shows that the mixing of σ C–H and σ* C–Cl in 2-chloro-2,3-dimethylbutane lowers the energy of both the orbitals (Figure 7).
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 ...