Conjugated system

In chemistry, a conjugated system is a system of connected p-orbitals with delocalized electrons in compounds with alternating single and multiple bonds, which in general may lower the overall energy of the molecule and increase stability. Lone pairs, radicals or carbenium ions may be part of the system. The compound may be cyclic, acyclic, linear or mixed. Conjugation is the overlap of one p-orbital with another across an intervening sigma bond (in larger atoms d-orbitals can be involved).

Quotes

 * The stability of a conjugated diene arises because of an interaction between the p orbitals of the two double bonds. To review briefly, when two p atomic orbitals combine to form a π bond, two π molecular orbitals (MOs) result. One is lower in energy than the starting p orbitals and is therefore bonding; the other is higher in energy, has a node between nuclei, and is antibonding. The two p electrons occupy the low-energy, bonding orbital, resulting in formation of a stable bond between atoms.
 * John McMurry, Organic Chemistry 8th ed. (2012), Ch. 14. Conjugated Compounds and Ultraviolet Spectroscopy


 * Dienes are named according to the rules formulated for ordinary alkenes. Conjugated dienes are more stable than dienes containing two isolated double bonds, as measured by their heats of hydrogenation. (...) The molecular-orbital picture of the π system in 1,3-butadiene shows two bonding and two antibonding orbitals. The four electrons are placed in the first two bonding levels.
 * K. Peter C. Vollhardt, Neil E. Schore (2011) Organic chemistry : structure and function 6th ed. Ch. 14 : Delocalized Pi Systems


 * Conjugated dienes are electron rich and are attacked by electrophiles to give intermediate allylic cations on the way to 1,2- and 1,4-addition products. These reactions may be subject to kinetic control at relatively low temperatures. At relatively higher temperatures, the kinetic product ratios may change to thermodynamic product ratios, when such product formation is reversible.
 * K. Peter C. Vollhardt, Neil E. Schore (2011) Organic chemistry : structure and function 6th ed. Ch. 14 : Delocalized Pi Systems


 * Conjugated dienes and hexatrienes are capable of (reversible) electrocyclic ring closures to cyclobutenes and 1,3-cyclohexadienes, respectively. The diene – cyclobutene system prefers thermal conrotatory and photochemical disrotatory modes. The triene – cyclohexadiene system reacts in the opposite way, proceeding through thermal disrotatory and photochemical conrotatory rearrangements. The stereochemistry of such electrocyclic reactions is governed by the Woodward-Hoffmann rules.
 * K. Peter C. Vollhardt, Neil E. Schore (2011) Organic chemistry : structure and function 6th ed. Ch. 14 : Delocalized Pi Systems


 * Cyclic conjugated polyenes are aromatic if their p electron count is 4n + 2. This number corresponds to a completely filled set of bonding molecular orbitals. Conversely, 4n p systems have open-shell, antiaromatic structures that are unstable, are reactive, and lack aromatic ring-current effects in 1H NMR. Finally, when steric constraints impose nonplanarity, cyclic polyenes behave as nonaromatic alkenes.
 * K. Peter C. Vollhardt, Neil E. Schore (2011) Organic chemistry : structure and function 6th ed. Ch. 15 : Benzene and Aromaticity