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Updated: Jul 15, 2026
A Strategy for Sensitive, Large Scale Quantitative Metabolomics
Published on: May 27, 2014
A cyclic carbanionic valence isomer of a carbocation: diphosphino analogs of diaminocarbocations
1Laboratoire d'Heterochimie Fondamentale et Appliquee, Universite Paul Sabatier, 118, route de Narbonne, F-31062 Toulouse cedex 04, France. Fakultat fur Chemie der Universitat, Postfach 10 01 31, D-33615 Bielefeld, Germany.
Abstract:
Diaminocarbocations (or amidinium salts) feature a three-center 4pi electron system with an open planar structure. Their 2pi 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.
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