HOMO-LUMO interaction strength

What does matter is the strength of the HOMO-LUMO interaction. In a nucleophilic attack on the carbonyl group, the nucleophile adds in to the low-energy n orbital. In a nucleophilic attack on a saturated carbon atom, the nucleophile must donate its electrons to the cr orbital of the C-X bond, as illustrated in the margin for an alkyl bromide reacting with the nonbonding lone pair of a nucleophile. 

When a molecule takes part in a reaction, it is properties at the molecular level which determine its chemical behaviour. Such intrinsic properties cannot be measured directly, however. What can be measured are macroscopic molecular properties which are likely to be manifestations of the intrinsic properties. It is therefore reasonable to assume that we can use macroscopic properties as probes on intrinsic properties. Through physical chemical models it is sometimes possible to relate macroscopic properties to intrinsic properties. For instance 13C NMR shifts can be used to estimate electron densities on different carbon atoms in a molecule. It is reasonable to expect that macroscopic observable properties which depend on the same intrinsic property will be more or less correlated to each other. It is also likely that observed properties which depend on different intrinsic properties will not be strongly correlated. A few examples illustrate this In a homologous series of compounds, the melting points and the boiling points are correlated. They depend on the strengths of intermolecular forces. To some extent such forces are due to van der Waals interactions, and hence, it is reasonable to assume a correlation also to the molar mass. Another example is furnished by the rather fuzzy concept nucleophilicity . What is usually meant by this term is the ability to donate electron density to an electron-deficient site. A number of measurable properties are related to this intrinsic property, e.g. refractive index, basicity as measured by pK, ionization potential, HOMO-LUMO energies, n — n ... 

The FMO definition also helps explain why Pearson s hard-hard and soft-soft interactions form stable complexes. Hard compounds have a large HOMO-LUMO gap, as shown in Figure 14.9 for F. Therefore, hard Lewis acid-base complexes tend to form strongly ionic compounds, such as LiF, where the interaction is dominated by electrostatic attractions. Soft compounds, on the other hand, have a small HOMO-LUMO gap, as shown in Figure 14.9 for I, so that these types of interactions form covalently bonded acid-base adducts, where the strength of the interaction is controlled primarily by the energies of the FMOs that participate in the bonding. 

The data indicate that the formation of cyclic intermediates creates a stabilization of the cationic chain ends (AH° < 0 and AH s < 0), also expressed by a decrease of both the acceptor strength (Ae(LUMO) > 0) and the donor strength (Ae(HOMO) < 0) of the cations. The positive charge of the cationic centre is distinctly decreased (Aqc+ < 0) as a consequence of the interaction of this centre with the oxygen of the methoxy group. A partially covalent C + —O-bond is formed (pt Q(f) > 0.6 rc+ 0if) 146 pm). 

In summary, one can identify three factors that mainly affect the epoxidation activity of a TM peroxo complex (i) the strength of the M-0 and 0-0 interactions, (ii) the electrophilidfy of the peroxo oxygen centers and the olefin, and (iii) the interaction between the tt(C-C) HOMO of the olefin and the peroxo a (0-0) orbital in the LUMO group of the metal complex to which we will also refer as the relevant unoccupied MO, RUMO (Figure 5). 

The cluster calculations for Li+, Na+, and K+ ions in six-membered windows (S,. and Sn sites) were performed by Beran (104). It was concluded that in this series the properties of a zeolite framework (charge distribution, bond orders, Lewis acidity or basicity as characterized by LUMO and HOMO energies) only slightly depend on the type of cation. The decrease of water adsorption heats in this sequence was explained by the assumption that the strength of the water-cation interaction correlates with the strength of the interaction between a cation and lattice oxygen atoms. 

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