Intramolecular donor-acceptor-interaction in N,N,N'-trimethyl-N'-halophosphinoethylendiamines and in N,N,N'-trimethyl-N'-difluoroarsinoethylendiamine

Abstract The reaction of Me2NCH2CH2N(Me)SiMe3 with MePCl2, ButPCl2 and AsF3 was found to proceed with formation of the trimethylsilyl halides, Me3SiX (X=Cl, F), and of the phosphorus-nitrogen (or arsenic-nitrogen)-bonded compounds, Me2NCH2CH2N(Me)P(Me)Cl, Me2NCH2CH2N(Me)P(But)Cl, and Me2NCH2CH2N(Me)AsF2, respectively. When PBr3, Et2NPCl2, and Et2NPBr2 were allowed to react with Me2NCH2CH2N(Me)SiMe3 the ionic, intramolecularly coordinated compounds, [Me2NCH2CH2N(Me)PBr]+Br−, [Me2NCH2CH2N(Me)PNEt2]+Cl, and [Me2NCH2CH2N(Me)PNET2]+ Br− were formed. The high- and low-temperature 1H- and 19F-n.m.r. spectra of these compounds were investigated. Their interaction with Lewis acids has been shown in the case of some acyclic, covalent phosphorylated derivatives of N.N.N′-trimethyl-ethylendiamine to induce intramolecular complexation between phosphorus and the nitrogen of the Me2N group. The spiro compound, [(Me2NCH2CH2N(Me))2P]+[BPh4]−, was obtained from the monocyclic product, [Me2NCH2CH2N(Me)PCl]+ Cl−, with Na[BPh...

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