Chemie der Phosphorfluoride. XXX. Reaktionen von N‐Trimethylsilylphosphiniminen mit Fluorphosphoranen: Synthese neuartiger Phosphiniminophosphoniumkationen

Abstract

N‐Trimethylsilylphosphinimine (CH3)3SiNPR′3 reagieren mit Fluorphosphoranen R2PF3 und RPF4 unter Abspaltung von Trimethylfluorsilan und Bildung von Phosphiniminophosphoniumkationen des Typs [RnP(NPR′3)4–n]+ (n = 1, 2; R = Fluor, Methyl, Phenyl; R′ = Methyl, Phenyl, Isopropyl) neben stabilen Fluorphosphatanionen der allgemeinen Formel [RnPF6–n]− (n = 1, 2; R = F, Methyl, Phenyl). Durch Umsetzung von N‐Trimethylsilylphosphiniminen mit Dimethyltrifluorphosphoran wurde das bisher unbekannte Dimethyltetrafluorphosphatanion [(CH3)2PF4]− neben den resonanzstabilisierten Phosphoniumkationen [(CH3)2P(NPR′3)2]+ erhalten. Die Strukturen der Reaktionsprodukte werden auf Grund der 1H, 19F und 31P NMR‐Spektren diskutiert.

Synthesis and NMR Investigation of Phosphineiminophosphonium Organofluorophosphate Salts

“…5 Results for the gegenions are unremarkable and are not reported in detail. With proton decoupling, the phosphorus spectra showed the expected first order patterns-AXz for I, AX3 for I11 and VII and AMXz for 11, IV, V, VI, and VIII.…”

Preparation and Properties of Dimethyltetrafluorophosphate

“…MePF 4 has typical properties of a Lewis acid, whereas the last member, Me 4 PF, serves as a source for “naked” fluoride. , Methyltetrafluorophosphorane reacts easily with alkali metal fluorides or Me 4 NF under formation of methylpentafluorophosphates (eq ) MePF 4 + MF → normalM + MePF 5 − 3em false( normalM = Cs , Me 4 normalN , Me 4 normalP false) In contrast to the well characterized MePF 5 − -anion, the homologous dimethyltetrafluorophosphate was described only as a product of the reaction of dimethyltrifluorophosphorane with N -trimethylsilylphosphine imines (eq ). − 2 Me 3 SiN = PR 3 + Me 2 PF 3 → false[ Me 2 normalP − false( normalN  PR 3 false) 2 false] + false[ Me 2 PF 4 false] − + Me 3 SiF 3em false( normalR = CH 3 , normalC …”

“…1 In contrast to the well characterized MePF 5 --anion, 1 the homologous dimethyltetrafluorophosphate was described only as a product of the reaction of dimethyltrifluorophosphorane with N-trimethylsilylphosphine imines (eq 2). [3][4][5][6] 2Me 3 SiN…”

The Crystal Molecular Structure of the Adduct of 2,2,2-Trifluoro-4,4,5,5-tetrakis(trifluoromethyl)-l,3,2A 5 -dioxaphospholane with Trimethylphosphine. A Strong P → P Coordinate Bond

“…2 is the first reported trifluorophosphorane-base adduct and demonstrates the powerful acceptor properties of 1 as compared to other substituted fluorophosphoranes. The W, and 31 P NMR data [7,8], for example the coupling constants 3 2 Jpf' = 118 Hz indicate the formation of the 'oxygen-trans' isomer, as there is adequate literature evidence [8][9][10] that vicinal coupling constants are strongly correlated with the dihedral angle at phosphorus and approach zero for angles of 180°…”