Synthesis and carbon tetrachloride reactions of (silylamino)phosphines

Abstract

In Section I, the reactions of a series of (silylamino)phosphines, (Me(,3)Si)(,2)NP(R)CHR'R'', with CCl(,4) are discussed. In general, two major reaction pathways are accessible for these reactions. Reaction pathway A involves removal of an (alpha) proton to produce an ylide intermediate, which then rearranges via a {1,3}-silyl migration to yield the corresponding P-chloro iminophosphorane, Me(,3)SiN=P(R)(Cl)-C(SiMe(,3))R'R'', in which the (alpha) carbon has become silylated. Reaction pathway B involves cleavage of a silicon-nitrogen bond by the CCl(,3)('-) anion to produce a P-chloro iminophosphorane, Me(,3)SiN=P(R)(Cl)-CHR'R'', which has one less silyl group. The factors which influence the course of such reactions are also discussed. In Section II, the preparation of a series of (Me(,3)Si)(,2)CH substituted (silylamino)phosphines, (Me(,3)Si)(,2)NP(R)CH(SiMe(,3))(,2), and, when applicable, their reactions with CCl(,4), are described. These phosphines showed varied reactivity which depended upon the other substituent (R) on phosphorus and/or the reaction conditions employed.