INTRAMOLECULAR DONOR-ACCEPTOR INTERACTIONS IN LAMBDA-(4)P(V) COMPOUNDS - PHOSPHORUS(V) DERIVATIVES OF N,N,N'-TRIMETHYLETHYLENEDIAMINE

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 (Formula Presented.) 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 (Formula Presented.) (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 (Formula Presented.) (NPh)NEt2]+ [BPh4]−1 (7). The methoxy‐λ3‐diazaphospholidinium salt [Me2 (Formula Presented.) 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] 22+2[BPh4]− (8), is isolated in low yield. Singlecrystal X‐ray structure determinations of 4 and 8 are described. Copyright © 1990 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim