A new method for the preparation of solution of sodium pentaphosphacyclopentadienide

Heating of a mixture of white phosphorus and sodium in diethylene glycol dimethyl ether in the presence of catalytic amounts of dibenzo-18-crown-6 affords a pure solution of sodium pentaphosphacyclopentadienide NaP₅. One of the intermediate products is trisodium heptaphosphide Na₃P₇. The influence of the nature of a metal (Li, Na, K) on the formation of the pentaphosphacyclopentadienide anion was studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1249–1251, July, 2006.     

A new route for the metallation of trihydroheptaphosphine P7H3 with butyllithium

A new route for the metallation of heptaphosphine P₇H₃ with BuLi, namely, decomposition of the nortricyclane P₇ unit to form dilithium hexadecaphosphide Li₂P₁₆, was found. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1247–1248, July, 2006.     

Trisodium heptaphosphide in reactions with cyclopropenyl complexes of nickel

Reactions of trisodium heptaphosphide with half-sandwich cyclopropenyl complexes of nickel gave sodium 1,2-diphosphacyclopentadienide. The influence of the ligand environment of the nickel atom on the formation of sodium 1,2-diphosphacyclopentadienide was studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 294–296, February, 2007.     

Chemistry of 1,2-diphospholide anions and 1,2-diphospholes

The main trends in the chemistry of 1,2-diphosphacyclopentadienes (1,2-diphospholes) and their derivatives 1,2-diphosphacyclopentadienide anions (1,2-diphospholide anions) were systematized, analyzed, and generalized. Methods for the generation of 1,2-diphospholide anions and their reactions with organic and organoelement electrophiles, as well as with transition metal complexes, were considered. Particular attention was paid to the cycloaddition reactions of 1-alkyl-1,2-diphospholes to obtain polycyclic chiral phosphines. A comparative analysis of the reactivity of 1,2-diphospholes and 1,2-diphospholide anions with respect to other representatives of phosphacyclopentadienes and phosphacyclopentadienide anions was carried out. The potential of application of 1,2-diphosphacyclopentadiene derivatives for the design of materials with magnetic, catalytic, and optical properties was shown.