Abstract: | Abstract The System CF3I/Me3P is re-investigated and Me2PCF3, Me4P+γ, (CF3)2PMe3, Me3PI2, Me3(CF3)P]+γ are found as products. Using CF3Br/P(NEt2)3 the phosphines R1 2PCF3 and R1P(CF3)2 (e.g. R1 = Me, iPr, NEt2) can be obtained which are precursors either for phosphoranes (e.g. 1,2λ5σ5-oxaphosphetanes) or phosphonium salts (e.g. R1 2(Me)PCF3]+X? or R1(Me)P(CF3)2X?]. The latter are deprotonated to furnish methylene phosphoranes R1 2(CH2=)PCF3 or R1(CH2=)P(CF3)2, reactive synthons. From CF3Br/P(NEt2)3/P(OPh)3 the phosphine P(CF3)3 is available, which turned out to be a potent electrophile. Amido phospites ROP(NEt2)2 and halides R2X (R2=CCl2CF3, X=Cl; R2=CF=CFCF3, X=F; R2=C6F5, X=Br, I; R2=C(CF3)3, X=Br; R2=SCF3, X=CF3) undergo an ARBUZOV reaction. |