Synthesis and characterization of new phosphanylium and phosphanetriylammonium salts. Molecular structures of [(Me2N)PN(AlCl3)R] and [P(NPri2)(NHR)]+[CF3SO3]–(R = C6H2But3-2,4,6)

Abstract

The new internal salts [(R¹R²N)PN(ECl₃)R](E = Al or Ga; R = 2,4,6-Bu^t₃C₆H₂) and phosphanylium salts [P(NR¹R²(NHR)]⁺[CF₃SO₃]^– have been synthesized by treating aminoiminophosphanes (R¹R²N)PNR with AlCl₃, GaCl₃or CF₃SO₃H. Protonation of RHN–PNR with trifluoromethanesulfonic acid led to the first stable phosphanylium salt [P(NHR)₂]⁺[CF₃SO₃]^– with two primary amino groups. In contrast, the reaction of AlCl₃ with the (aryloxy)iminophosphane (R′O)PNR (R′= 4-Me-2,6-Bu^t₂,C₆H₂) led to the new aryl(phosphanetriyl)ammonium complex [PNR]⁺[(R′O)AlCl₃]^–. All compounds were characterized by multinuclear NMR spectroscopy. The crystal structures of [(Me₂N)PN(AlCl₃)R] and [P(NPrⁱ₂)(NHR)]⁺[CF₃SO₃]^– have been determined by single-crystal X-ray diffractometry