Frontier formation

Tillmann, R.W. Almon, W.R. (1979) Diagehesis of Frontier Formation offshore bar sandstones. Spearhead Ranch field, Wyoming. In Aspects of Diagenesis (Eds Scholle, P.A. Schluger, P.R.). Spec. Publ. Soc. Econ. Paleont. Miner., Tulsa, 26, 337-378. 

Emphasis was put on providing a sound physicochemical basis for the modeling of the effects determining a reaction mechanism. Thus, methods were developed for the estimation of pXj-vahies, bond dissociation energies, heats of formation, frontier molecular orbital energies and coefficients, and stcric hindrance. 

The positively charged allyl cation would be expected to be the electron acceptor in any initial interaction with ethylene. Therefore, to consider this reaction in terms of frontier orbital theory, the question we need to answer is, do the ethylene HOMO and allyl cation LUMO interact favorably as the reactants approach one another The orbitals that are involved are shown in Fig. 1.27. If we analyze a symmetrical approach, which would be necessary for the simultaneous formation of the two new bonds, we see that the symmetries of the two orbitals do not match. Any bonding interaction developing at one end would be canceled by an antibonding interaction at the other end. The conclusion that is drawn from this analysis is that this particular reaction process is not favorable. We would need to consider other modes of approach to analyze the problem more thoroughly, but this analysis indicates that simultaneous (concerted) bond formation between ethylene and an allyl cation to form a cyclopentyl cation is not possible. 

A theoretical study based on PM3 frontier molecular orbital (FMO) and potential energy surface (PES) analysis at the RHF/6-31-I-G level was performed to examine the reaction of l-amino-2-ethoxycarbonylpyridinium mesitylenesulfonate and acrylonitrile in the presence of Hiinig s base leading to the formation of 3-cyano-4-hydroxy-l,2-dihydropyrido[l,2-ft]pyridazi-nium inner salt (54) (99JOC9001). The calculations indicated that both the... 

The [2 + 2] photodimerization of a, j8-unsaturated sulfones is correctly viewed as a photoreaction of alkenes, rather than the sulfone group, and this aspect has been reviewed recently by Reid, as part of a wider survey of the photoreaction of O- and S-heterocycles. The topic continues to attract considerable interest and a few recent examples, as well as some synthetic applications, will be discussed here. Much of the photodimerization work has been carried out on the benzo[fc]thiophene (thianaphthene) 1,1-dioxide system. For example. Porter and coworkers have shown that both 3-carboxybenzo[i]thiophene 1,1-dioxide (65) and its methyl ester give only the head-to-head (hth), anti dimer (66) on irradiation in ethanol. In a rather unusual finding for such systems, the same dimer was obtained on thermal dimerization of 65. Similar findings for a much wider variety of 3-substituted benzo[fi]thiophene 1,1-dioxides have been reported more recently by Geneste and coworkers . In the 2-substituted analogs, the hth dimer is accompanied by some of the head-to-tail (htt), anti dimer. The formation of the major dimer appears to proceed by way of an excited triplet and the regiochemistry observed is in accord with frontier MO theory. 

On the other hand, many pericyclic reactions are accelerated by Lewis-acid catalysts. The acceleration has been attributed to a complex formation between the Lewis acid and the polar groups of the reactants that brings about changes in the energies and orbital coefficients of the frontier orbitals.6 The complex formation also stabilizes the enhanced polarized transition state. 

In the same year as that of the proposal of the frontier-electron theory, the theory of charge-transfer force was developed by Mulliken with regard to the molecular complex formation between an electron donor and an acceptor 47>. In this connection he proposed the "overlap and orientation principle 48> in which only the overlap interaction between the HO MO of the donor and the LU MO of the acceptor is considered. 

The value vr is regarded as a measure of the extent to which the electron in the rth AO takes part in the bond formation with other atoms. In contrast with this, pT is the part of population in the rth AO which is living there and responsible for the interaction with outside. Hence, in view of the role of the frontier orbital in the charge-transfer interaction, it is reasonable to take, as the frontier density, the valence-inactive part 7S>. Namely,... 

There are some advantages of the temporal models of cloud chemistry associated with the concentrations of molecules at different times. Can we learn about the age of the cloud by its chemical composition or the age of an embedded star by the chemistry observed towards the object Can the molecular environment be understood from the inventory of chemicals Are there chemical diagnostics for planetary formation, star formation or even black holes All of these questions are at the frontier of Astrochemistry. 

On descending the sub-group the colour generally becomes lighter, indicating an increased separation between the frontier orbitals, which are believed to be predominantly associated with the metal frame, and therefore a decrease of the metallic character. The overall constancy of the values of the enthalpies of formation of these compounds, and the use of an estimated sublimation enthalpy of ca. 

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