Lewis structures alternative

None of the atoms in the Lewis structure shown in step 6 possesses a formal charge An alternative Lewis structure for methyl nitrite... 

It IS good chemical practice to represent molecules by their most stable Lewis structure The ability to write alternative resonance forms and to compare their relative stabilities however can provide insight into both molecular structure and chemical behavior This will become particularly apparent m the last two thirds of this text where the resonance concept will be used regularly... 

In order to predict the structure of the product, you must identify the factors that will tend to favor selective ketal formation. Consider selective carbonyl protonation first. Obtain energies and atomic charges, and display electrostatic potential maps of the alternative protonated ketones (protonated ketone A, protonated ketone B). Identify the more stable isomer. Compare geometries and draw whatever Lewis structures are needed to account for your data. Why is one isomer more stable than the other Is the more stable isomer also that in which the positive charge is better delocalized Will the more stable isomer undergo nucleophilic attack more or less easily than the other Explain. 

Draw a Lewis structure for cyclohexenone that involves charge separation for the most polar bond. Then, draw a Lewis structure that will delocalize one or both charges. Next, examine the actual geometry of cyclohexenone. Are the bond distances consistent with the Lewis structure shown above, or have they altered in accord with your alternative (charge separated) Lewis structure (Structures for cyclohexene and cyclohexanone are available for reference.)... 

Examine the eleetrostatic potential map of eaeh nueleophile (enamine, silyl enol ether, lithium enolate and enol) with emphasis on the face of the nucleophilic alkene carbon. Rank the nucleophiles from most electron rich to least electron rich. What factors are responsible for this order (Hint For each molecule, consider an alternative Lewis structure to that given above that places a negative charge on the nucleophilic carbon.)... 

Examine the geometry and atomic charges of 2-pyridone to see if it is localized as indicated in the drawing above, or delocalized (as in 2-hydroxypyridine). If you need to, write alternative Lewis structures to that provided above. How many n electrons does 2-pyridone possess Is 2-pyridone aromatic ... 

It is possible to write a simple Lewis structure for foe S042- ion, involving only single bonds, which follows foe octet rule. However, Linus Pauling and others have suggested an alternative structure, involving double bonds, in which foe sulfur atom is surrounded by six electron pairs. 

Benzene, C6H(l, is another molecule best described as a resonance hybrid. It consists of a planar hexagonal ring of six carbon atoms, each one having a hydrogen atom attached to it. One Lewis structure that contributes to the resonance hybrid is shown in (11) it is called a Kekulc structure. The structure is normally written as a line structure (see Section C), a simple hexagon with alternating single and double lines (12). 

J 5 Use formal charge calculations to evaluate alternative Lewis structures (Toolbox 2.2 and Examples 2.6 and 2.8). 

Borazine, B3N3Hft, a compound that has been called inorganic benzene because of its similar hexagonal structure (but with alternating B and N atoms in place of C atoms), is the basis of a large class of boron—nitrogen compounds. Write its Lewis structure and predict the composition of the hybrid orbitals used by each B and N atom. 

Kekule structures Two Lewis structures of benzene, consisting of alternating single and double bonds, kelvin (K) The SI unit of temperature. See also Appendix IB. 

C21-0047. Boron nitride (BN) is a planar covalent solid analogous to graphite. Write a portion of the Lewis structure and describe the bonding of boron nitride, which has alternating B and N atoms. 

The many higher boranes such as B5H9 and BgH 2 are similarly electron deficient and cannot be described by a single Lewis structure. They can often be described in terms of a combination of two- and three-center bonds. Alternatively, their structures can be rationalized by electron-counting schemes such as those proposed by Wade. Analysis of the electron density of these molecules by the AIM method shows that there are bond paths between all adjacent pairs of atoms. So from the point of view of the AIM theory there are bonds between each adjacent pair of atoms, but these cannot all be regarded as Lewis two-center, two-electron bonds as is the case in B2H6. 

Although the most naive form of valence-bond and Lewis-structure theory would not predict the paramagnetism of O2, the VB-like NBO donor-acceptor perspective allows us to develop an alternative localized picture of general wavefunctions, including those of MO type. Let us therefore seek to develop a general NBO-based configurational picture of homonuclear diatomics to complement the usual MO description. 

To achieve non-zero 7ta—7tb conjugation, the pi NBOs of 18 may polarize in opposite directions, leading to a wavefunction of lower symmetry than the nuclear framework. Alternatively, the nuclear framework may distort to diamond-like D2h geometry. However, each such distortion destabilizes what is already a highly unfavorable Lewis-structure wavefunction, so cyclobutadiene is expected to remain highly destabilized relative to other possible polyene topologies. 

However, the relative accuracies of the two possible structural bond patterns can be assessed more quantitatively with NBO analysis. The NBO procedure allows one to specify alternative Lewis structure patterns of two- and three-center bonds158 and determine the non-Lewis density error pni, of each such structure. As shown in Table 3.41(a), the non-Lewis density of the 4012 structure (0.6072c) is smaller than that of the 3103 structure (0.8760c), which confirms that the 4012 structure (3.248) is indeed the superior bonding description in this case. 

Although the generalization to localized three-center bonds inevitably involves certain complications, important simplifications of the localized Lewis-structure picture remain. In the case of 3c/4e co-bonding, the corrections can often be adequately described in terms of two-term resonance between alternative two-center bonding patterns. In the case of 3c/2e T-bonding, the resonance-theoretic description (although possible in principle) becomes unwieldy. However, in terms of the single best three-center localized Lewis-structure description (or the resonance mixture of symmetry-equivalent structures), one can still identify specific localized donor-acceptor interactions (e.g., of type) that dominate the delocaliza-... 

As noted above (note 111), geminal NBO delocalizations may be associated with alternative resonance structures related to (3.181). Hence, this structure might better be considered to depict geminal hyperconjugative corrections to the classical single-bonded Lewis structure. 

The accuracy of alternative Lewis structures can be assessed by specifying the number and locations of lone pairs and two- and three-center bonds with a SCHOOSE keylist (a standard option of the NBO program). (The directed SCHOOSE list replaces the usual NBO search over all possible Lewis structures, but the hybrids and polarization coefficients of CHOOSE structures are optimized in the usual way.) The increased non-Lewis density measures the larger error of the CHOOSE structure compared with the optimal NBO structure. 

Alternatively, we can also analyze the TS complex with respect to NBOs of the product-like Lewis structure (by using the standard SCHOOSE option of the NBO program). Figure 5.59(a) depicts an alternative view of the TS geometry, with bond sticks drawn to emphasize the relationship to the product cyclohexene molecule. Figures 5.59(b)-(d) depict the leading donor-acceptor stabilizations in the product NBO Lewis structure. 

When you begin a Lewis structure, do not place identical atoms adjacent to each other unless there is no alternative. Carbon is the only common exception. Most compounds containing more than one carbon atom will have the carbon atoms adjacent to each other. 

The molecular orbital picture of benzene proposes that the six jt electrons are no longer associated with particular bonds, but are effectively delocalized over the whole molecule, spread out via orbitals that span all six carbons. This picture allows us to appreciate the enhanced stability of an aromatic ring, and also, in due course, to understand the reactivity of aromatic systems. There is an alternative approach based on Lewis structures that is also of particular value in helping us to understand chemical behaviour. Because this method is simple and easy to apply, it is an approach we shall use frequently. This approach is based on what we term resonance structures. 

A carbocation in which a group or moiety bridges two or more potential carbenium centers (such that there are alternative Lewis structures having different carbenium centers). 

Fig. 14.1. Lewis structures of the carboxylate ion. (a) and (b) Two equivalent symmetry breaking structures, (c) An alternative Lewis structure, (d) The average of (a) and (b) which preserves the inherent S3nnmetry of the ion.

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