Electron delocalizations

The immediate site of the adsorbent-adsorbate interaction is presumably that between adjacent atoms of the respective species. This is certainly true in chemisorption, where actual chemical bond formation is the rule, and is largely true in the case of physical adsorption, with the possible exception of multilayer formation, which can be viewed as a consequence of weak, long-range force helds. Another possible exception would be the case of molecules where some electron delocalization is present, as with aromatic ring systems. 

Electron delocalization can be important in ions as well as in neutral molecules Using curved arrows show how an equally stable resonance structure can be generated for each of the following anions... 

Electron delocalization stabilizes a molecule A molecule in which electrons are delocalized is more stable than implied by any of the individual Lewis structures that may be written for it The de gree of stabilization is greatest when the contrib uting Lewis structures are of equal stability... 

Nitromethane is stabilized by electron delocalization more than methyl nitrite is The two most stable resonance forms of nitromethane are equivalent to each other... 

These are the most important rules to be concerned with at present Additional aspects of electron delocalization as well as additional rules for Its depiction by way of resonance structures will be developed as needed in subsequent chapters... 

Electron Delocalization in the Conjugate Base With a of —1 4 nitnc acid is almost completely ionized m water If we look at the Lewis structure of nitric acid m light of what we have said about inductive effects we can see why The N atom m nitric acid IS not only electronegative m its own right but bears a formal charge of +1 which enhances its ability to attract electrons away from the —OH group... 

Nitrate ion is stabilized by electron delocalization which we can represent m terms of resonance between three equivalent Lewis structures... 

The negative charge is shared equally by all three oxygens Stabilization of nitrate ion by electron delocalization increases the equilibrium constant for its formation... 

A similar electron delocalization stabilizes acetate ion and related species... 

Electron delocalization m the conjugate base usually expressed via resonance between Lewis structures increases acidity... 

Of the two conformations of ethane the staggered is 12 kJImol (2 9 heal mol) more stable than the eclipsed The staggered conformation is the most stable conformation the eclipsed is the least stable conformation Two main explanations have been offered for the difference in stability between the two conformations One explanation holds that repulsions between bonds on adjacent atoms destabilize the eclipsed conformation The other suggests that better electron delocalization stabilizes the staggered conformation The latter of these two explanations is now believed to be the correct one... 

Electron delocalization m allylic carbocations can be indicated using a dashed line to show the sharing of a pair of rr electrons by the three carbons The structural formula IS completed by placing a positive charge above the dashed line or by adding partial pos itive charges to the carbons at the end of the allylic system... 

An orbital overlap description of electron delocalization mil dimethylallyl cation H2C=CH—C(CH3)2 is given m Figure 10 2 Figure 10 2a shows the rr bond and the vacant p orbital as independent units Figure 10 2b shows how the units can overlap to give an extended rr orbital that encompasses all three carbons This permits the two rr electrons to be delocalized over three carbons and disperses the positive charge... 

Just as allyl cation is stabilized by electron delocalization so is allyl radical... 

Breaking a bond to a primary hydrogen atom m propene requires less energy by 42 kJ/mol (10 kcal/mol) than m propane The free radical produced from propene is allylic and stabilized by electron delocalization the one from propane is not... 

Additional evidence for electron delocalization m 1 3 butadiene can be obtained by considering its conformations Overlap of the two rr electron systems is optimal when the four carbon atoms are coplanar Two conformations allow this coplananty they are called the s cis and s trans conformations... 

Section 10 7 Conjugated dienes are stabilized by electron delocalization to the extent of 12-16 kJ/mol (3 kcal/mol) Overlap of the p orbitals of four adja cent sp hybridized carbons in a conjugated diene gives an extended tt system through which the electrons are delocalized... 

We attributed the decreased bond dissociation energy in propene to stabilization of allyl radical by electron delocalization Similarly electron delocalization stabilizes benzyl rad ical and weakens the benzylic C—H bond... 

During our discussion of benzene and its derivatives it may have occurred to you that cyclobutadiene and cyclooctatetraene might be stabilized by cyclic rr electron delocal ization m a manner analogous to that of benzene... 

A second isomer of [lOJannulene (the cis trans cis cis trans stereoisomer) can have bond angles close to 120° but is destabilized by a close contact between two hydro gens directed toward the interior of the ring To minimize the van der Waals strain between these hydrogens the nng adopts a nonplanar geometry which limits its ability to be stabilized by tt electron delocalization It too has been prepared and is not very stable Similarly the next higher (4n + 2) system [14]annulene is also somewhat desta bilized by van der Waals strain and is nonplanar... 

The carbocation is aromatic the hydrocarbon is not Although cycloheptatriene has six TT electrons m a conjugated system the ends of the triene system are separated by an sp hybridized carbon which prevents continuous tt electron delocalization... 

Here liberties have been taken with the Robinson symbol Instead of restricting its use to a sextet of electrons organic chemists have come to adopt it as an all purpose sym bol for cyclic electron delocalization... 

Section 11 14 Benzylic carbocations are intermediates in SnI reactions of benzylic halides and are stabilized by electron delocalization... 

The carbocation formed m this step is a cyclohexadienyl cation Other commonly used terms include arenium ion and a complex It is an allylic carbocation and is stabilized by electron delocalization which can be represented by resonance... 

One way to assess the relative stabilities of these various intermediates is to exam me electron delocalization m them using a resonance description The cyclohexadienyl cations leading to o and p mtrotoluene have tertiary carbocation character Each has a resonance form m which the positive charge resides on the carbon that bears the methyl group... 

Aldol condensation offers an effective route to a p unsaturated aldehydes and ketones These compounds have some interesting properties that result from conjugation of the carbon-carbon double bond with the carbonyl group As shown m Figure 18 6 the rr systems of the carbon-carbon and carbon-oxygen double bonds overlap to form an extended rr system that permits increased electron delocalization... 

This electron delocalization stabilizes a conjugated system Under conditions cho sen to bring about their mterconversion the equilibrium between a p 7 unsaturated ketone and an a p unsaturated analog favors the conjugated isomer... 

In resonance terms electron delocalization map unsaturated carbonyl compounds IS represented by contributions from three principal resonance structures... 

Additionally sp hybridization of the hydroxyl oxygen allows one of its unshared electron pairs to be delocalized by orbital overlap with the tt system of the carbonyl group (Figure 19 1) In resonance terms this electron delocalization is represented as... 

The resonance effect of the carbonyl group Electron delocalization expressed by resonance between the following Lewis structures causes the negative charge in acetate to be shared equally by both oxygens Electron delocalization of this type IS not available to ethoxide ion... 

Electron delocalization in carboxylate ions is nicely illustrated with the aid of elec trostatic potential maps As Figure 19 4 shows the electrostatic potential is different for the two different oxygens of acetic acid but is the same for the two equivalent oxygens of acetate ion... 

Notice too that the carbonyl oxygen of the carboxylic acid is protonated m the first step and not the hydroxyl oxygen The species formed by protonation of the car bonyl oxygen is more stable because it is stabilized by electron delocalization The pos itive charge is shared equally by both oxygens... 

Electron delocalization in carbonyl protonated benzoic acid... 

Resonance description of electron delocalization in carboxylate anion... 

Workrng against this electron delocalization is the fact that both carbonyl groups are competing for the same electron parr Thus the extent to which each one is stabilized is reduced... 

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