Isolobal principle

The isolobal principle (also known as isolobal analogy) is way to predict bonding properties of organometallic compounds. In organometallic chemistry, it relates the structure of organic ligands that can bind to inorganic molecular fragments. Roald Hoffmann described molecular fragments as isolobal "if the number, symmetry properties, approximate energy and shape of the frontier orbitals and the number of electrons in them are similar – not identical, but similar." One can predict the bonding and reactivity of a lesser-known pieces from that of a better-known pieces if the two molecular fragments have similar frontier orbitals, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Isolobal compounds are analogs to isoelectronic compounds that share the same number of valence electrons and structure. A graphic representation of isolobal structures, with the isolobal pairs connected through a double-headed arrow with half an orbital below, is found in Figure 1.

Figure 1: Basic example of the isolobal analogy.

For his work on the isolobal analogy, Hoffmann was awarded the Nobel Prize in Chemistry in 1981, which he shared with Kenichi Fukui. In his Nobel Prize lecture, Hoffmann stressed that the isolobal analogy is a useful, yet simple, model. It does fail in certain instances.

Isolobal Principle Media

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  'Figure 3: Production of a frontier orbital in an octahedral complex. Since the process is not charge producing, the metal center must change from d6 Mo to d7 Mn to retain the neutral charge.

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  Figure 4: Isolobal fragments of tetrahedral and octahedral geometries. The d- electrons configuration is wrong. It is d8 ML4 and d9 ML3.

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  Figure 5: Molecular orbital diagram depiction of frontier orbitals in methane and a basic ML6 metal complex

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  Figure 8: Examples of non-basic shapes in the isolobal analogy.