Resonant Term

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... 

In resonance terms the shorter carbon-oxygen bond distance in phenol is attrib uted to the partial double bond character that results from conjugation of the unshared electron pair of oxygen with the aromatic ring... 

The stabilizing role of other functional groups can also be described in resonance terms. Both electron-attracting groups such as carbonyl and cyano and electron-donating groups such as methoxy and dimethylamino have a stabilizing etfect on a radical intermediate at an adjacent carbon. The resonance structures which depict these interactions indicate delocalization of the unpaired electron onto the adjacent substituents ... 

Because all six carbon atoms and all six p orbitals in benzene are equivalent, it s impossible lo define three localized tt bonds in which a given p orbital overlaps only one neighboring p orbital. Rather, each p orbital overlaps equally well with both neighboring p orbitals, leading to a picture of benzene in which the six -tt electrons are completely delocalized around the ring. In resonance terms (Sections 2.4 and 2.5), benzene is a hybrid of two equivalent forms. Neither form... 

In contrast with amines, amides (RCONH ) are nonbasic. Amides don t undergo substantial protonation by aqueous acids, and they are poor nucleophiles. The main reason for this difference in basicity between amines and amides is that an amide is stabilized by delocalization of the nitrogen lone-pair electrons through orbital overlap with the carbonyl group. In resonance terms, amides are more stable and less reactive than amines because they are hybrids of two resonance forms. This amide resonance stabilization is lost when the nitrogen atom is protonated, so protonation is disfavored. Electrostatic potential maps show clearly the decreased electron density on the amide nitrogen. 

As noted previously, arylamines are generally less basic than alkylamines. Anilinium ion has pKa = 4.63, for instance, whereas methylammonium ion has pfCa = 10.64. Arylamines are less basic than alkylamines because the nitrogen lone-pair electrons are delocalized by interaction with the aromatic ring tt electron system and are less available for bonding to H+. In resonance terms, aryl-amines are stabilized relative to alkylamines because of their five resonance forms. 

The main resonance terms for a single electron-pair bond are those involving only one eigenfunction from each atom. 

In graphite each carbon atom is bound to three others in the same plane and here the assumption of inversion of a puckered layer is improbable, because of the number of atoms involved. A probable structure is one in which each carbon atom forms two single bonds and one double bond with other atoms. These three bonds should lie in a plane, with angles 109°28 and 125°16,l which are not far from 120°. Two single bonds and a double bond should be nearly as stable as four single bonds (in diamond), and the stability would be increased by the resonance terms arising from the shift of the double bond from one atom to another. But this problem and the closely related problem of the structure of aromatic nuclei demand a detailed discussion, perhaps along the lines indicated, before they can be considered to be solved. 

It has been found that a simple and powerful approximate method of treatment of bond orbitals can be developed by assuming that the dependence on r of s, p, and d orbitals corresponding to about the same energy is nearly the same, so that the r-portion of the resonance terms can be taken as the same. The consideration of the ft, q> portion of the orbitals then leads directly to the determination of the best bond orbitals which can be formed under given circumstances. 

The amplitudes y are generally complex and the relative phase between the resonant term and the background term determines the precise line-shape that will be observed. An alternative to Eq. (6) makes use of the sum form ... 

As it concerns the band in the UV region (at 315 nm in the present case), Benesi and Hildebrand [5] assigned this absorption to a charge-transfer transition, where the phenyl ring acts as an electron donor (D) and the iodine as an electron acceptor. The interaction can be described in resonance terms as D-I2 <-> D+I2", the band being assigned to the transition from the ground non polar state to the excited polar state. 

The consistency of the oscillator strength for all three materials indicates that the only difference in the experimental results for each case are the resonance terms due to changes in u>gi and u)gf. The large oscillator strengths are an intrinsic... 

The most fruitful treatment of the electronic effects of ozt/zo-substituents involves the use of the same cr/ and correlation analysis for meta- and para-substituents by means of the dual substituent-parameter equation 91 or the extended Hammett equation 95 (Section II.B). Obviously it is a considerable assumption that these are valid for ort/zo-substituents and the implication is that in the correlation analysis any peculiarities may be adequately expressed through the coefficients of the inductive and resonance terms. Really satisfactory correlation analysis for any given reaction system requires a large amount of data and can only rarely be accomplished. 

Taft and Topsom s article151 and also Topsom s171 should be consulted for details of the setting up of the scales of substituent parameters. The equation has been applied to a wide range of gas-phase reactivities. (In the multiple regressions an intercept term is often permitted, but usually this turns out to be indistinguishable from zero, as it should be if equation 20 is valid.) For aliphatic and alicyclic saturated systems the resonance term is duly negligible. The roles of field, resonance and polarizability effects are discussed and the interpretat of the various p values is attempted. 

Here, the sum is over all possible resonance vectors. Since the leading contribution to 0,(f) is co,t, it follows that near the particular resonance m of interest, other phase factors in Eq. (3.29) will be oscillatory functions of time while due to Eq. (3.27), exp(/m 0) will be slowly varying. Retaining only the one resonance term in Eq. (3.29),... 

An extension of the latter type of interaction may be found in, for example, the suggestion that in the Silicon tetrahalides the central atom 3d orbitals act as r-acceptors for the lone pair electrons on the halogen atoms. In resonance terms this amounts to the contribution of the ionic double-bond structures to the ground state of the molecule (Fig. 4). 

In. a number of cases sub-maxima associated with vXH bands have been interpreted in this fashion and in the case of the carboxylic acid dimers this question has been investigated in some detail [4]. A prominent satellite band accompanying the main vOH bands has been assigned to an overtone of the <5QH vibration, and it has been possible to explain formally most of the multiplicity of peaks in the rOH band of formic acid in Fermi resonance terms. Although it is possible that some of these peaks correspond to Stepanov-type sub-bands, no convincing series of this type can be picked out. There seems little doubt that in many cases a considerable number of sub-bands in the rXH region are to be interpreted in terms of Fermi resonance [5, 43,... 

Table 9.8 illustrates the second main feature of selectivity in abstraction of hydrogen. Polar substituents affect the product distribution, but do so differently for different abstracting radicals.142 Chlorine atoms attack a hydrogen on a carbon already bearing chlorine less rapidly than on one that does not, whereas phenyl radicals behave in just the opposite way and bromine atoms are intermediate. The explanation is that the chlorine atom is electrophilic and its attack will be hindered by electron withdrawal. In resonance terms, there is an im-... 

---