A ROUTE TO NOVEL FUNCTIONALIZED BIS(IMINO)PHOSPHORANES XP(=NARYL)=NALKYL

Chloro(arylimino)phosphane (1) reacts with alkyl azides RN3 (R = tBu, Et3C, 1-Ad) to form 4,5-dihydro-1H-tetrazaphospholes 2a-c. The thermal decomposition of these compounds results in the formation of the diazadiphosphetidines 4a-c via the chlorobis(imino)phosphorane intermediates 3a-c, which were detected by NMR spectroscopy. By treating 2a with the lithium salts Li(nBu, C5Me5, NHAryl, OAryl, tBuS) the 4,5-dihydro-1H-tetrazaphosphole intermediates 5a-d are obtained, which by elimination of nitrogen form the bis(imino)phosphoranes 6a-e. The X-ray structure determination of the phosphane derivative tBu2P-P( = NCEt3) = NAryl (7), obtained by the same procedure, is discussed.