M. R. Marre

EXTENSION OF THE STAUDINGER REACTION TO THE PHOSPHENIUM CATION [—P—]+: SYNTHESIS OF A NEW CLASS OF TETRAVALENT TRICOORDINATED PHOSPHORUS CATIONS

Abstract Three types of P[dbnd]N phosphazene bonds are known: and R3 P[dbnd]N—R. here classified according to the coordination numbers: 2,3,4 and valences 3,5,5, respectively. In this communication we describe a new phosphazene bond in a cation having a coordination number three and valence four:

Phosphazene spirannique a partir de derives du phophore dicoordine

The reaction of azidoalcohol 2 on triazaphosphole 1 takes place according to pathway a and not b, as shown by the isolation of spirannic phosphazene 3. The diazadiphosphetidines 4, dimers of 3 are also caracterized.

ENANTIOSPECIFIC SYNTHESIS OF PENTACOORDINATED PHOSPHORUS COMPOUNDS X-RAYS DIFFRACTION STRUCTURE AND REACTION MECHANISM

Abstract It is shown that the synthesis of the optically active spirophosphorane 5 is enantiospecific. The structure and the configuration of the enantiomeric pure diastereoisomer, given by the reaction, has been established by X-rays diffraction. A mechanism accounting for the stereospecificity is proposed. The same selectivity has been observed for three other compounds.

Phosphocations with co-ordination number 2 and 3 : phosphenium–iminophosphonium bisphosphocations

New phosphocations containing phosphorus with co-ordination number 2 and 3 and deriving from Cl–P–NR2 AlCl4- have been obtained: chloroiminophosphonium compounds (2) and the bisphosphocations (phosphenium–iminophosphoniums)(3).

CATIONS PHOSPHORES A BASSE COORDINATION: LES IMINOPHOSPHENIUMS N[sbnd]p[sbnd]N[dbnd]NR

Abstract The novel iminophosphenium, [(CH3)2N]2 P+=NC6H5, has been prepared by a modified Staudinger reaction. The mechanism of this process is discussed on the basis of spectroscopic studies of various derivatives of this ion.

Study of the P bond in phosphorimidates by 15N and 31p spectroscopy

Abstract The P-N double bond character in phosphorimidates is discussed in terms of 1JP-N coupling and δ15N or δ31P chemical shifts.