C. Malavaud

Formation of stable cyclic dicoordinated phosphorus compounds by reaction of cyclophosphazanes with lewis acids

Abstract Thermal equilibrium between dicoordinated and tricoordinated phosphorus compounds (i.e. benzodiazaphosphole ⇄cyclotetraphosphazane) has been observed. The dicoordinated compounds have been stabilized by complexing with Lewis acid and isolated.

Action des composes dicarbonyles-1,2 sur des composes du phosphore dicoordonne a liaison pn et sur leurs oligomeres.

Abstract Triazaphospholes react with 1,2-diketones to give spirocyclic phosphorus compounds by a 1.1 addition at phosphorus atom; with o-quinones one obtains spirobicyclic hexacoordinated phosphorus compounds. The reaction of 1,2-diketones with λ 3 -phosphazene oligomers appears different, to some extent, and can be used as a test for the existence of a monomer-oligomer equilibrium.

Composes du phosphore dicoordonne: Reaction de diaza-1,4 dienes-1,3 disubstitues sur les derives de diazaphosphole. Du triazaphosphole-1,2,4,3 et de precurseurs de composes du phosphore dicoordonne

Addition of diazadienes 5 to dicoordinated phosphorus derivatives such as triazaphospholes 1 or diazaphospholes 3 leads to new tetracoordinated phosphorus spirocompounds 2 or 4. The tricoordinated phosphorus species 7 and 9 exist in a monomer tetramer PIII equilibrium but only the monomeric PII form reacts with diazadienes 5 leading to the spirocompounds 8 and 10. The monomers of 7 and 9 stabilized by complexation react with 5 to afford spirocompounds analogous to 2 and 4. In all these reactions the dicoordinated phosphorus atom is a good electrophile.

Composes du phosphore dicoordonne. Les bitriazaphospholes-1,2,4,3: Synthese et proprietes

Resume The title compounds were obtained by reaction of diamidrazones with tris(dimethylamino)phosphine. The bitriazaphosphole structure is consistent with mass spectra. The reactivity of these new compounds and of triazaphosphole derivatives seems to be the same.

Is the previously described N-phenyl 4,5-benzo 1,3,2-diazaphosphole a dicoordinated phosphorus compound ?

Abstract Dicoordinated Phosphorus; 1,3,2-Diazaphospholes; Cyclotetraphosphazanes. The N-phenyl 4,5-benzo 1,3,2-diazaphosphole 1 cannot be isolated free but can be identified in complexed form. It polymerizes and gives first a cyclotetraphosphazane, then quickly a polymer. It is depolymerized by a Lewis acid AlCl3; this complex reacts as a dicoordinated phosphorus compound.