A Cyclic Carbanionic Valence Isomer of a Carbocation: Diphosphino Analogs of Diaminocarbocations

Abstract

Diaminocarbocations (or amidinium salts) feature a three-center 4π electron system with an open planar structure. Their 2π electron three-membered cyclic valence isomers, in which the carbon atom bears a negative charge, are predicted to be about 541 kilojoules per mole higher in energy than the open form. This isomer has not been identified yet. In contrast, the attempted synthesis of a diphosphorus analog of amidinium salts leads to the cyclic carbanionic form. There is no precedent for such a transformation of a carbocationic center into a carbanionic center, but with the help of heavier main-group elements, numerous examples can be imagined. This approach will enable the preparation of many unknown structural moieties that are difficult or even impossible to access in the corresponding carbon and nitrogen series.