Preparation and chemistry of penta- and hexacoordinated phosphorus compounds containing trifluoroethoxy groups

The Reaction of Alkyl Phosphites With 3,5-Di-Tert-Butyl-1,2-Benzoquinone. Variable Temperature NMR Studies on New Pentaoxyphosphoranes

“…pentaoxyphosphorane 4 which is derived from the symmetrically hindered 3,6-ditert-butyl-1,Zbenzoquinone (3). This study is now extended to include new pentaoxyphosphoranes of type 7, which are derived from the asymmetrically hindered 3,5-di-tert-butyl-l,2-benzoquinone (S), in order to gain more knowledge about the factors affecting pseudorotation in these monocyclic pentaoxyphosphorane systems.…”

A duality of mechanism in the hydrolysis of acyclic phosphoranes

“…The reaction of three-co-ordinate phosphorus compounds (l), n = 0-3, with 2,2,2-trifluoroethyl phenylsulphenate (2) is now a well established and efficient route to acyclic phosphoranes (3) [reaction (1)l.I The reaction must be carried out in aprotic and preferably non-polar media (e.g. toluene) since the phosphoranes, although thermally stable, are sensitive to moisture.…”

Controlled Synthesis of Polyphosphazenes with Chain-Capping Agents

“…This high field resonance arises from the hexacoordinate species (CF 3 CH 2 O) 6 P − , in which the phosphorus center carries a formal negative charge. This compound was previously prepared and its 31 P-NMR chemical shift was reported as −154.6 ppm [ 46 ]. Electronegative groups stabilize the phosphorus hexacoordinated state [ 47 ].…”

“…Its chemical shift of −72 ppm is typical of five-coordinate phosphorus compounds as previously reported [ 45 ], and sufficiently electronegative ligands tend to stabilize such species [ 45 ]. The penta-(2,2,2-trifluoroethoxy) phosphorane, P(OCH 2 CF 3 ) 5 , was previously prepared and its 31 P-NMR chemical shift reported as −76.6 ppm [ 46 ]. Another example of a penta-coordinated phosphorus compound with an N -benzyl ligand is (CF 3 ) 3 (F)P[N(CH 3 ) (CH 2 Ph)] with a δp = −68.8 ppm [ 48 ].…”