A wide variety of the title compounds were prepared by reaction of the Grignard reagents, (Me(3)Si)(n)CH3-nMgCl (n = 1, 2), or the alkyllithium reagent, Me(3)SiCH(Ph)Li, with PCl3, PhPCl(2), or Me(2)-NP(R)Cl (R = Ph, t-Bu), followed by addition of Me(3)SiNMe(2) and/or LiOCH2CF3. The PNMe(2) derivatives were converted to the chlorophosphine analogs, Me(3)SiCH(2)P(R)Cl (R = Ph, t-Bu), by reaction with PCl3 or HCl. In some cases, mixtures of diastereomers result from the presence of chiral centers at both. phosphorus and carbon.