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Difluorocarbene which is quantitatively eliminated from donor-free bis(trifluoromethyl)- cadmium below 0 °C inserts smoothly into the P-F bonds of PF5 to form (CF 3 ) 3  PF 2  in high yield. Due to the fast conversion of P-Cl bonds into P-F bonds by cadmium fluoride, PCl 5  forms (CF 3 ) 3 PF 2  as well, and a direct synthesis of (CF 3 ) 3 PF 2  with ca. 70 % yield starting from CdEt 2 , CF 3 I and PCl 5  is reported. Whereas no insertion of CF 2  into the axial bonds of (CF 3 ) 3 PF2 has been detected, reaction of (CF 3 )2Cd with (CF 3 ) 3  PCl 2  gives the new tetrakis( haloalkyl)fluorophosphoranes (CF  ) 3  (CF 2 C 1 )PF, (CF 3 ) 3  (CFCl 2  )PF, (CF 3 ) 2  (CF 2 Cl) 2 PF and (CF 3 ) 3  (CCl 3 )PF. The NMR spectra of these and related compounds and of their hydrolysis products (CF 3 ) 3 (CF 3-n Cl n )PO are reported. The formation of the higher chlorinated phosphoranes is discussed in terms of an isomerization mechanism presumably involving carbene elimination-reinsertion processes.

zeitschrift für naturforschung b

Reaktionen des donorfreien (CF 3 ) 2 Cd mit Phosphor(V)halogeniden: Difluorcarben-Einschiebungen und Direktsynthese von (CF 3 ) 3 PF 2  / Reactions of Donor-Free (CF 3 ) 2 Cd with Phosphorus(V) Halides: Insertion of Difluorocarbene and Direct Synthesis of (CF 3 ) 3 PF 2