Intramolekulare Donator‐Akzeptorwechselwirkungen in λ 4 P(V)‐Verbindungen Phosphor(V)‐Derivate des N,N,N ′‐Trimethylethylendiamins

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