13 C and 31 P NMR studies of some aminophosphonium chlorides

The multinuclear NMR spectral data for an homologous series of tertiary phosphines, R 3‐n P(NMe 2 ) n , aminophos‐phonium ions, [R 3 PNR′R″] + , and phosphonium ions, [R 4‐n PMe] + , where R = Me, Et, n ‐Pr and Ph, R′ and/or R″ = H, Me and n = 0 and 1 are reported and discussed. Quaternization by alkylation or chloramination causes an increase in the 31 P chemical shift (Δ δ P is positive), a decrease in the 13 C chemical shift (Δ δ C is negative) for all carbons, an increase in the magnitudes of 1 J (PC), 3 J (PC), 3 J (PNCH) and 2 J (PCH) and a decrease in the magnitude of 2 J (PC). Substitution of a Me 2 N group for an alkyl or aryl group produces an increase in the 31 P chemical shift and in the magnitude of 1 J (PC). α‐ and β‐deshielding and γ‐shielding effects are noted in the 13 C NMR spectra and β‐deshielding and γ‐shielding effects are noted in the 31 P NMR spectra with substitution on the phosphorus and nitrogen atoms.