Carbocation

A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium CH3+, methanium CH5+ and vinyl C2H3+ cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encountered (e.g., ethylene dication C2H42+). Until the early 1970s, all carbocations were called carbonium ions. In the present-day definition given by the IUPAC, a carbocation is any even-electron cation with significant partial positive charge on a carbon atom. They are further classified in two main categories according to the coordination number of the charged carbon: three in the carbenium ions and five in the carbonium ions. This nomenclature was proposed by G. A. Olah. Carbonium ions, as originally defined by Olah, are characterized by a three-center two-electron delocalized bonding scheme and are essentially synonymous with so-called 'non-classical carbocations', which are carbocations that contain bridging C–C or C–H σ-bonds. However, others have more narrowly defined the term 'carbonium ion' as formally protonated or alkylated alkanes (CR5+, where R is H or alkyl), to the exclusion of non-classical carbocations like the 2-norbornyl cation. According to the IUPAC, a carbocation is any cation containing an even number of electrons in which a significant portion of the positive charge resides on a carbon atom. Prior to the observation of five-coordinate carbocations by Olah and coworkers, carbocation and carbonium ion were used interchangeably. Olah proposed a redefinition of carbonium ion as a carbocation featuring any type of three-center two-electron bonding, while a carbenium ion was newly coined to refer to a carbocation containing only two-center two-electron bonds with a three-coordinate positive carbon. Subsequently, others have used the term carbonium ion more narrowly to refer to species that are derived (at least formally) from electrophilic attack of H+ or R+ on an alkane, in analogy to other main group onium species, while a carbocation that contains any type of three-centered bonding is referred to as a non-classical carbocation.