Another way the Lewis-Acid base concept is widely employed for understanding chemical reactivity is through the frontier orbital approach to chemical reactions. The frontier orbital concept conceptualizes chemical bonding and reactivity in terms of the interactions between frontier orbitals on the chemical species undergoing an interaction ( e.g. molecules, atoms, ions, or groups as they interact to form a bond or undergo a reaction). Frontier orbitals are those at the frontier between occupied and unoccupied. They are often taken to be the h ighest energy o ccupied and l owest energy u noccupied molecular orbitals, called the HOMO and LUMO levels. However, it can sometimes be more convenient to think about them as atomic orbitals or Valence Bond approach-derived orbitals. When developing rough qualitative frontier orbital descriptions of the orbital interactions involved in a given system, the choice of what types of orbitals to use is often a matter of what is the most informative and convenient. In particular, the frontier orbital concept envisions a Lewis acid-base interaction as involving an interaction between some of the frontier orbitals of the Lewis acid and base, specifically the donation of electrons from the base's HOMO level into the acid's LUMO level. For example, in the frontier orbital approach, adduct formation between \(NH_3\) and \(BH_3\) involves the donation of electrons from ammonia's a 1 HOMO into BH 3 's a 2 '' LUMO level. As expected when two orbitals of the appropriate symmetry combine, the result of the interaction is the formation of a lower energy bonding orbital between the acid and base (Figure \( \PageIndex{1}\)). Since it is occupied by an electron, the net result of the interaction is the lowering of the base's lone pair energy as it interacts with the Lewis acid. In this case the interaction just follows the general pattern for Lewis-Acid base adduct formation, which is: The frontier orbital concept illuminates the orbital interactions involved in reactions. For instance, from a frontier orbital perspective the alkyl halide substitution reaction between hydroxide and CH 3 Cl via the S N 2 mechanism involves a Lewis acid-base interaction: Notice how the frontier orbital approach even explains the displacement of the chloride leaving group. The donation of electrons from the hydroxide HOMO populates the antibonding CH 3 Cl LUMO, breaking the C-Cl bond. With the frontier orbital approach, it becomes apparent that pericyclic reactions are Lewis acid-base reactions. For example, in the Diels-Alder reaction, the dienophile acts as a Lewis base and the diene as a Lewis acid. The orbital interactions involved in a given reaction can include both reactants acting as both an acid and base. In these cases the HOMO of each reactant interacts with the LUMO of the other. A good example of this involves \( \Pi \)-type interactions between a metal ion with occupied d orbitals and a pi-acceptor ligand. The ligand acts as a base and the metal as an acid to give a M-CO single bond: However, the metal can also act as a base towards the ligand LUMO ( \( \pi ^*\) ) orbitals. The frontier orbital concept can also be used to describe interactions between one or more singly occupied frontier orbitals. In fact, when approximate molecular orbital diagrams are being constructed, it can often be helpful to focus on one or two particularly instructive interactions. In these cases, it is sometimes convenient to think about a chemical bond as involving the formation of bonding and antibonding interactions between singly occupied frontier orbitals on different molecular fragments. For instance, when thinking about the chemistry of \(CH_3Re(CO)_5\) it can sometimes be helpful to think about the C-Re bond as arising from the interaction between a singly-occupied sp 3 type orbital on a CH 3 group and a singly occupied d 2 sp 3 orbital on the Re. In introducing singly occupied orbitals, the frontier orbital concept formally handles interactions that the Lewis acid-base concept does not, since Lewis acid-base behavior is formally confined to the acceptance and donation of electron pairs .