Abstract
Many compounds can be represented well in terms of the two-center–two-electron (2c–2e) bond model. However, it is well-known that this approach has limitations; for example, certain compounds require the use of three-center–two-electron (3c–2e) bonds to provide an adequate description of the bonding. Although a classic example of a compound that features a 3c–2e bond is provided by diborane, B2H6, 3c–2e interactions also feature prominently in transition metal chemistry, as exemplified by bridging hydride compounds, agostic compounds, dihydrogen complexes, and hydrocarbon and silane σ-complexes. In addition to being able to identify the different types of bonds (2c–2e and 3c–2e) present in a molecule, it is essential to be able to utilize these models to evaluate the chemical reasonableness of a molecule by applying the octet and 18-electron rules; however, to do so requires determination of the electron counts of atoms in molecules. Although this is easily achieved for molecules that possess only 2c–2e bonds, the situation is more complex for those that possess 3c–2e bonds. Therefore, this article describes a convenient approach for representing 3c–2e interactions in a manner that facilitates the electron counting procedure for such compounds. In particular, specific attention is devoted to the use of the half-arrow formalism to represent 3c–2e interactions in compounds with bridging hydrogen atoms.
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