论文信息 - Intramolekulare Donator‐Akzeptorwechselwirkungen in λ4P(V)‐Verbindungen Phosphor(V)‐Derivate des N,N,N′‐Trimethylethylendiamins

Intramolekulare Donator‐Akzeptorwechselwirkungen in λ4P(V)‐Verbindungen Phosphor(V)‐Derivate des N,N,N′‐Trimethylethylendiamins

Intramolecular Donor-Acceptor Interactions in λ4P(V) Compounds. — Phosphorus(V) Derivatives of N,N,N′-Trimethyl-ethylenediamine The chlorophosphino derivative of N,N,N′-trimethylethyl-enediamine Me2NCH2CH2(Me)NP(Cl)Me (1) and the 2-(diethylamino)-λ3-phospholidinium salt [Me2 NEt2]+ Cl− (5) have been allowed to react with several oxidizing agents. Reaction of 1 with dimethyl sulfoxide furnishes the phosphonamidic chloride Me2NCH2CH2(Me)NP(O)(Cl)Me (3) while with elemental sulfur the phosphonamidothioic chloride Me2NCH2CH2(Me)NP(S)(Cl)Me (2) is obtained. The reaction of 2 with sodium tetraphenylborate furnished the 1,1,2,3-tetramethyl-1,3,2-λ4-diazaphospholidinium tetraphenylborate [Me2 (S)Me]+ [BPh4]− (4). The reaction of 5 with phenyl azide, followed by sodium tetraphenylborate led to 2-(diethylamino)-2-(phenylimino)-1,3,2λ4-diazaphospholidinium tetraphenylborate [Me2 (NPh)NEt2]+ [BPh4]−1 (7). The methoxy-λ3-diazaphospholidinium salt [Me2 OMe]+ [BPh4]− (6) does not react with phenyl azide to produce the 2-methoxy-2-(phenylimino)-1,3,2λ4-diaza-phospholidinium salt analogous to 7; instead its rearrangement product, the dimeric 1,3,2λ4,4λ4-diazadiphosphetidine tetraphenylborate [Me3NCH2CH2(Me)NP(O)NPh]2[BPh4]− (8), is isolated in low yield. Singlecrystal X-ray structure determinations of 4 and 8 are described.

P. G. Jones | W. Becker | Peter G. Jones | D. Schomburg | R. Schmutzler

[1] R. Schmutzler,et al. Über intramolekulare Donator-Akzeptor-Wechselwirkungen in N,N′-Dimethylharnstoff-Derivaten des Phosphors / Intramolecular Donor-Acceptor Interactions in N,N′-Dimethylurea Derivatives of Phosphorus , 1989 .

[2] W. Becker,et al. ÜBER DIE UMSETZUNG VON N,N,N′-TRIMETHYLN-HALOGENPHOSPHINO-ETHYLENDIAMINEN MIT NATRIUMTETRAPHENYLBORAT UND ALUMINIUMCHLORID: DARSTELLUNG VON INTRAMOLEKULAREN KOMPLEXEN MIT λ3-PHOSPHOR(III) , 1989 .

[3] R. Schmutzler,et al. Intramolecular donor-acceptor-interaction in N,N,N'-trimethyl-N'-halophosphinoethylendiamines and in N,N,N'-trimethyl-N'-difluoroarsinoethylendiamine , 1988 .

[4] D. Schomburg,et al. 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(C6 H5)2, (CH3)2NCH2CH2N(CH3)P(C6 H5)Cl UND (C , 1986 .

[5] Y. Gololobov,et al. Sixty years of staudinger reaction , 1981 .

[6] J. Springer,et al. Characterization and molecular structure of 1-hydro-2,8,9-trioxa-1-phospha-5-aza-tricyclo[3.3.3.0]undecane tetrafluoroborate. Pentacoordination of phosphorus , 2002 .

[7] D. D. Perrin,et al. Purification of laboratory chemicals , 1966 .