On the metallic nature of carbon in allenes and heterocumulenes

The IUPAC defines allenes as organic compounds having at least two double bonds from one carbon to two others. Thus the central carbon atom is in accord with the octet rule through the formation of two σ and two π bonds. However, this perspective highlights a series of recent experimental, as well as theoretical results, suggesting that depending on the substituents, this canonical description might not be the most adequate. In fact, in a growing number of examples the bond in allenes and related heterocumulenes is better described as an inner carbon that plays the role of the central atom of a "coordination complex" and interacts with its substituents as if they were ligands of this organic complex. This interpretation of the bond in allenes is especially useful in predicting the C(0), carbene or partial carbocationic character of the central carbon atom.