72 / 2023-09-06 02:59:37

Phosphacyclopentadienide anions – building blocks for organophosphorus chemistry

phospholes,phosphorus,Phosphacyclopentadienide,phosphaferrocenes,asymmetric catalysis,elemental phosphorus

New Technologies in Phosphorus Chemistry > 1) New reagents and methods in organophosphorus Chemistry

Phosphacyclopentadienide (phospholide) anions and their derivatives are very attractive as building blocks for the construction of versatile organophosphorus molecular materials with useful and interesting catalytic, optical, luminescent, and magnetic properties.^[1] Therefore, development of convenient methods for the straightforward synthesis of these phosphorus heterocycles and their derivatives through functionalization of elemental phosphorus P₄ (bypassing toxic chlorine Cl₂) has a significant interest.^[2] This lecture features recent advances on the synthesis of various phosphacyclopentadienide anions and their chemical behavior toward organic or organoelement substrates, and transition metal complexes. A rational and highly efficient method to access 1-mono-,^[3] 1,2-di-^[4] and 1,2,3-triphospholide^[5] anions in individual forms directly from white phosphorus P₄, alkali metals and small molecules (alkynes and cyclopropenylium halides) have been developed. Interaction with various chiral and non-chiral alkyl halides has resulted in the formation of novel P-heterocycles, namely 1-mono-, 1,2-di- and 1,2,3-triphospholes. Reaction with iron(II) complexes was used as a convenient way for an efficient synthesis of a number of new phosphaferrocenes.^[6] First results on the application in materials science and homogeneous catalysis of phospholide derivatives (phospholes and their [4+2] cycloadducts) were also reported.^[7] This work was supported by the Russian Science Foundation (project no. 21-73-10204).