Synthesis of Ammonium‐ and 4‐Dimethylaminopyridinium Amidofluorophosphates and Crystal Structure of [DMAPH][PO₂F(NH₂)]

Abstract

NH 4 [PO 2 F(NH 2 )] has been prepared by the reaction of a betaine py·PO 2 F with excess ammonia in acetonitrile solution, while the ammonolysis of DMAP·PO 2 F with a stoichiometric amount of NH 3 yields [DMAPH][PO 2 F(NH 2 )]. The crystal structure of the latter was determined by single-crystal X-ray diffraction, which revealed that the anions [PO 2 F(NH 2 )] Ϫ are linked to infinite chains by double NϪH···O bridges. Additional strong NϪH···O Synthese von Ammonium-und 4-Dimethylaminopyridinium-Amidofluorophosphaten und die Kristallstruktur von [DMAPH][PO 2 F(NH 2 )]Inhaltsübersicht. NH 4 [PO 2 F(NH 2 )] wurde durch Umsetzung des Betains py·PO 2 F in acetonitrilischer Lösung mit überschüssigem NH 3 dargestellt, während bei der Ammonolyse von DMAP·PO 2 F mit einer stöchiometrischen Menge von Ammoniak [DMAPH]-[PO 2 F(NH 2 )] entsteht. In der Kristallstruktur von [DMAPH]-[PO 2 F(NH 2 )] sind die Anionen durch doppelte Wasserstoff-Brü-* Dr. Miloš Č erník

Review of Heteroleptic Tetrahedra as Birefringent or Nonlinear Optical Motifs

“…First is the introduction of monomers F/NH 2 /S into MO 4 (M = Be, B, Al, Si, P, S) to constitute the heteroleptic tetrahedra BO x X 4– x (X = F, NH 2 ; x = 1, 2, 3), PO x F 4– x ( x = 2, 3), PO l F m (NH 2 ) n ( l + m + n = 4), SiO x F 4– x ( x = 2, 3), and MO x X 4– x (M = Be, Al, S; X = F, NH 2 , N; x = 1, 2, 3). Among them, heteroleptic tetrahedra BO x F 4– x ( x = 1, 2, 3), PO x F 4– x ( x = 2, 3), MO 3 F (M = Be, Al, S), ,, and PO 2 F­(NH 2 ) , have been reported by experimental. Typically, heteroleptic tetrahedron PO 2 F­(NH 2 ) appears in amidofluorophosphates APO 2 F­(NH 2 ) (A = K, NH 4 ) and [DMAPH]­PO 2 F­(NH 2 ). , Reference also mentioned the heteroleptic tetrahedra POS­(NH 2 ) 2 , PO 2 S­(NH 2 ), and SO 3 (NH 2 ).…”

“…Among them, heteroleptic tetrahedra BO x F 4– x ( x = 1, 2, 3), PO x F 4– x ( x = 2, 3), MO 3 F (M = Be, Al, S), ,, and PO 2 F­(NH 2 ) , have been reported by experimental. Typically, heteroleptic tetrahedron PO 2 F­(NH 2 ) appears in amidofluorophosphates APO 2 F­(NH 2 ) (A = K, NH 4 ) and [DMAPH]­PO 2 F­(NH 2 ). , Reference also mentioned the heteroleptic tetrahedra POS­(NH 2 ) 2 , PO 2 S­(NH 2 ), and SO 3 (NH 2 ). Fluorooxo-functional groups SiO x F 4– x ( x = 2, 3) have not been discovered in fluorooxosilicates so far.…”

“…Typically, heteroleptic tetrahedron PO 2 F(NH 2 ) appears in amidofluorophosphates APO 2 F-(NH 2 ) (A = K, NH 4 ) and [DMAPH]PO 2 F(NH 2 ). 95,96 Reference 95 also mentioned the heteroleptic tetrahedra POS(NH 2 ) 2 , PO 2 S(NH 2 ), and SO 3 (NH 2 ). Fluorooxo-functional groups SiO x F 4−x (x = 2, 3) have not been discovered in fluorooxosilicates so far.…”