6069-01-8Relevant academic research and scientific papers
Vibrational spectra, conformations, and intramolecular interactions of R(CH2)2-O-PCl2 molecules (R = Et, OMe)
Katsyuba,Schmutzler,Avvakumova,Vandyukov,Alfonsov,Melnicky
, p. 13 - 25 (1999)
IR and Raman spectroscopy, normal coordinate analysis, and molecular mechanics were used to study the conformations of R(CH2)2-O-PCl2 molecules (R = Et, OMe). It is shown that in the case of R = Et, that the molecules prefer to exist in more or less extended conformations, R and PCl2 groups being spatially far apart. In contrast, the convoluted conformations are preferred in the case of R = OMe. In these conformations the intramolecular distances between nonbonded P1 and O5 atoms are comparable with the sums of the corresponding van der Waal's radii. The substantial energetical preference of the convoluted conformations in the liquid state is assigned to certain attractive intramolecular 1-5 interactions between the phosphorus and the oxygen atoms. The energy of the interaction may amount to ~2-4.5 kcal mo-1.
UEBER DIE UMSETZUNG VON N- BZW. O-TRIMETHYLSILYLIERTEN DERIVATEN DES ETHANOLAMINS MIT PHOSPHOR(III)-HALOGEN-VERBINDUNGEN: INTRAMOLEKULARE DONATOR-AKZEPTOR-WECHSELWIRKUNGEN IN DEN VERBINDUNGEN CH3OCH2CH2N(CH3)PCl2, (CH3)2NCH2CH2OPCl2, (CH3)2NCH2CH2N(CH3)P(C6H5)2, ...
Bettermann, Gerhard,Schomburg, Dietmar,Schmutzler, Reinhard
, p. 327 - 336 (2007/10/02)
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-Si or O-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 CH2CH2N(Me)PCl>(1+)*Cl(1-), 3a.The reversibleformation 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 phophorus 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 has established its identity as an intramolecular complex.The X-ray structure determination proved the existence of a tricoordinate phosphorus atom with a rather short covalent P-N bond with a bond-distance of 162 pm and a short coordinative P-N bond of 184,2 pm.No interaction of the second chlorine with phosphorus was observed.
