TRIS(DIALKYLAMINO)PHOSPHINE WITH PYRAMIDAL NITROGENS

Syntheses for the unstable symmetrical tricyclic aminophosphine 1 and its relatively stable O=P (2). S=P (3), and Se=P (4) derivatives are reported. The failure of 1 to form a stable BH3 adduct contrasts with that observed for P(NMe2)3. P(MeNCH2bCMe, and P([formula omitted]CH2h and is rationalized in terms of electronic differences on the nitrogen which are imposed by structural constraints. The trend in lJpsc for these compounds is shown to be consistent with this idea. The structure of 3, determined by X-ray means, substantiates our earlier postulate that constraint in P(ZC)3 systems decreases the PZC angle before the ZPZ angle is affected. © 1979, American Chemical Society. All rights reserved.