Leaving group

In chemistry, a leaving group is defined by the IUPAC as an atom or group of atoms that detaches from the main or residual part of a substrate during a reaction or elementary step of a reaction.^[1] However, in common usage, the term is often limited to a fragment that departs with a pair of electrons in heterolytic bond cleavage.^[2] In this usage, a leaving group is a less formal but more commonly used synonym of the term nucleofuge. In this context, leaving groups are generally anions or neutral species, departing from neutral or cationic substrates, respectively, though in rare cases, cations leaving from a dicationic substrate are also known.^[3]

A species' ability to serve as a leaving group depends on its ability to stabilize the additional electron density that results from bond heterolysis. Common anionic leaving groups are halides such as Cl⁻, Br⁻ and I⁻, and sulfonate esters such as tosylate (TsO⁻), while water (H₂O), alcohols (R−OH), and amines (R₃N) are common neutral leaving groups.

In the broader IUPAC definition, the term also includes groups that depart without an electron pair in a heterolytic cleavage (groups specifically known as an electrofuges), like H⁺ or SiR+3, which commonly depart in electrophilic aromatic substitution reactions.^[1][4] Similarly, species of high thermodynamic stability like nitrogen (N₂) or carbon dioxide (CO₂) commonly act as leaving groups in homolytic bond cleavage reactions of radical species. A relatively uncommon term that serves as the antonym of leaving group is entering group (i.e., a species that reacts with and forms a bond with a substrate or a substrate-derived intermediate).

In this article, the discussions below mainly pertain to leaving groups that act as nucleofuges.