ÜBER DIE UMSETZUNG VON N- BZW. O-TRIMETHYLSILYLIERTEN DERIVATEN DES ETHANOLAMINS MIT PHOSPHOR(III)-HALOGEN-VERBINDUNGEN: INTRAMOLEKULARE DONATOR-AKZEPTOR-WECHSEL WIRKUNGEN IN DEN VERBINDUNGEN CH3OCH2CH2N(CH3)PCl2, (CH3)2NCH2CH2OPCl2, (CH3)2NCH2CH2N(CH3)P(C6H5)2, (CH3)2NCH2CH2N(CH3)P(C6H5)Cl UND (CH3)2NCH2CH2N(CH3)PCl2

Abstract

Abstract The reaction of MeOCH2CH2N(Me)SiMe3, Me2NCH2CH2OSiMe3, and Me2NCH2CH2N(Me)SiMe3 with PCl3. PhPCl2, and Ph2PCl was found to proceed with cleavage of the N[sbnd]Si or O[sbnd]Si bond and formation of the phosphorus(III) compounds, 3 to 8. In this series of, in part, novel phosphorus(III) compounds an intramolecular donor-acceptor interaction between NMe2 substituents and phosphorus has been observed which in the case of the product of the reaction of Me2NCH2CH2N(Me)SiMe3 with PCl3, led to a stable intramolecular complex, , 3a. The reversible formation of an intramolecular complex, as a function of temperature, has been observed for Me2NCH2CH2N(Me)P(Ph)Cl,4 while no evidence for an intramolecular interaction was noted for compounds 5, 6 and 8. For compound 7 which is obtained as a solid an intramolecular interaction between phosphorus and nitrogen seems likely in the solid state but cannot be observed by n.m.r. spectroscopy in solution in CDCl3. A single crystal X-ray structure determination for 3a h...