Application of Molecular Orbital Theory to Reactivity

Another aspect of qualitative application of MO theory is the analysis of interactions of the orbitals in reacting molecules. As molecules approach one another and reaction proceeds, there is a mutual perturbation of the orbitals. This process continues until the reaction is complete and the new product (or intermediate in a multistep reaction) is formed. PMO theory incorporates the concept of frontier orbital control. This concept proposes that the most important interactions will be between a particular pair of orbitals. These orbitals are the highest filled oihital of one reactant (the HOMO, highest occupied molecular oihital) and the lowest unfilled (LUMO, lowest unoccupied molecular oihital) orbital of the other reactant. The basis for concentrating attention on these two orbitals is that they will be the closest in energy of the interacting orbitals. A basic postulate of PMO 

Coulson and H. C. Longuet-lliy gina, Proc. R. Soc. London, Ser. A 192 16 (1947) L. Sal m, J. Am. Chem. Soc. 90 543 (1968) M. J. S. Dewar and R. C. Dougherty, The PMO Theory of Organic Chemistry, Plenum Press, New VlMk, 1975 G. Klopman, Chemical Reactivity and Reaction Paths, Wiley-Interscience, New Yoik, 1974, Chapter 4. 

4 57 (1971) I. Fleming, Frontier Orbital and Organic Chemical Reactions, John Vfiiey St Sons, New Yodt, 1976 L. Salem, Electrons in Chemical Reactions, John Wil Sons, New Yoric, 1982, Chapter 6. 

SECTION 1.6. APPLICATION OF MOLECULAR ORBITAL THEORY TO REACTIVITY 

Interaction of f. irmeilileliyde frontier orbitals with E and Nu Fig. 1.25. PMO description of interaction of ethylene and formaldehyde with an electrophile (E ) and a nucleophile (Nu ). 

It MO energy levels for ethylene with a n-donor substituent. 

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The other two chapters deal with the application of molecular orbital theory to heterocyclic chemistry. The groups surveyed are (a) sulfur heterocycles and (6) azines. The chapters, which are authored by R. Zahradnik and J. Koutecky, discuss the relevance of theoretical calculation to reactivity, electronic structure, and other physicochemical properties of the compounds. The new techniques of theoretical chemistry have been applied with great success to carbocyclic compounds their significance in heterocyclic chemistry will surely increase. 

The application of molecular orbital theory to carbanions was discussed by Nobes, R. H. Poppinger, D. Li, W.-K. Radom, L. in Buncel, E. Durst, T., Eds. Comprehensive Carbanion Chemistry. Part C. Ground and Excited State Reactivity Elsevier Amsterdam, 1987 pp. 1-92. 

Both the language of valence bond theory and of molecular orbital theory are used in discussing structural effects on reactivity and mechanism. Our intent is to illustrate both approaches to interpretation. A decade has passed since the publication of the Third Edition. That decade has seen significant developments in areas covered by the text. Perhaps most noteworthy has been the application of computational methods to a much wider range of problems of structure and mechanism. We have updated the description of computational methods and have included examples throughout the text of application of computational methods to specific reactions. 

The chemical potential, chemical hardness and sofmess, and reactivity indices have been nsed by a number of workers to assess a priori the reactivity of chemical species from their intrinsic electronic properties. Perhaps one of the most successful and best known methods is the frontier orbital theory of Fukui [1,2]. Developed further by Parr and Yang [3], the method relates the reactivity of a molecule with respect to electrophilic or nucleophilic attack to the charge density arising from the highest occupied molecular orbital or lowest unoccupied molecular orbital, respectively. Parr and coworkers [4,5] were able to use these Fukui indices to deduce the hard and soft (Lewis) acids and bases principle from theoretical principles, providing one of the first applications of electronic structure theory to explain chemical reactivity. In essentially the same form, the Fukui functions (FFs) were used to predict the molecular chemical reactivity of a number of systems including Diels-Alder condensations [6,7], monosubstituted benzenes [8], as well as a number of model compounds [9,10]. Recent applications are too numerous to catalog here but include silylenes [11], pyridinium ions [12], and indoles [13]. 

The above work has also led to the prediction that the so-called -effect for nucleophiles containing a heteroatom adjacent to the reaction centre should display normal behaviour in the gas phase (Wolfe et al., 1981a,b, 1982). This prediction has been corroborated by recent experimental determinations that show little variation of reactivity between HOO- and HO (DePuy et al., 1983), contrary to what is predicted by the application of frontier molecular orbital theory (Fleming, 1976). 

The structural requirements of the mesomeric betaines described in Section III endow these molecules with reactive -electron systems whose orbital symmetries are suitable for participation in a variety of pericyclic reactions. In particular, many betaines undergo 1,3-dipolar cycloaddition reactions giving stable adducts. Since these reactions are moderately exothermic, the transition state can be expected to occur early in the reaction and the magnitude of the frontier orbital interactions, as 1,3-dipole and 1,3-dipolarophile approach, can be expected to influence the energy of the transition state—and therefore the reaction rate and the structure of the product. This is the essence of frontier molecular orbital (EMO) theory, several accounts of which have been published. 16.317 application of the FMO method to the pericyclic reactions of mesomeric betaines has met with considerable success. The following section describes how the reactivity, electroselectivity, and regioselectivity of these molecules have been rationalized. 

The BIDE theory does not explain all observed experimental results. Addition reactions are not adequately handled at all, mosdy owing to steric and electronic effects in the transition state. Thus it is important to consider both the reactivities of the radical and the intended coreactant or environment in any attempt to predict the course of a radical reaction (18). Application of frontier molecular orbital theory may be more appropriate to explain certain reactions (19). 

Scheme 3-5). Ohya-Nishiguchi et al. (1980) noted that such a large localized spin density is very rare in a ir-electron system of purine s size and should have important application to its chemical reactivity. Reactions such as protonation should take place preferentially at position 6. This was deduced from the result of molecular orbital calculations (Nakajima Pullman 1959). According to Fukui s frontier electron theory (Fukui et al. 1952), such areaction should take place at the position where the frontier electron density is the largest. The calculations clearly indicate that the large electron density is at position 6. Scheme 3-5 describes the protonation of the purine anion radical (Yao Musha 1974). Protonation indeed takes place at position 6. After that, the radical center appears at the cyclic nitrogen in the vicinal 1 position.

The development of molecular orbital (MO) techniques and their applications to structural and reactivity problems in surface chemistry were improved by density functional theory (DFT) methods. In the case of semiempirical MO methods, symmetry arguments in structural chemistry and reactivity were provided however, DFT has allowed theoretical chemistry to predict accurately the structures of clusters in surfaces and organometallic compounds. 

In contrast to the claim (10) that the ECW model "disguises the relationship between reactivity and periodic elemental properties", elementary application of frontier molecular orbital theory (H) can be used to understand the trends. Using qualitative trends in ionization energies, inductive effects, electronegativities and partial charge/size ratios, one can estimate trends in the HOMO-LUMO separation of the donor and acceptor. Increasing the separation decreases the covalent and increases the electrostatic nature of the interaction. Decreasing the separation has the opposite effect. Trends in the reported acid and base parameters as well as in the Ey E0 and C C0 products can be understood in this way. 

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