The System CF 3 I/Me 3 P is re-investigated and Me 2 PCF 3 , Me4P + I", (CF 3 )2PMe 3 , Me 3 PI 2 , [Me 3 (CF 3 )P] + r are found as products. Using CF 3 Br/P(NEt2)3 the phosphines R 1 2 PCF 3 and R 1 P(CF 3 ) 2 (e.g. R 1 = Me, iPr, NEt 2 ) can be obtained which are precursors either for phosphoranes (e.g. l,2^5a 5 -oxaphosphetanes) or phosphonium salts (e.g. [R 1 2 (Me)PCF 3 ] + X" or [R 1 (Me)P(CF 3 )2X"]. The latter are deprotonated to furnish methylene phosphoranes R 1 2 (CH2=)PCF 3 or R 1 (CH 2 =)P(CF3) 2 , reactive synthons. From CF 3 Br/ P(NEt 2 )3/P(OPh) 3 the phosphine P(CF 3 ) 3 is available, which turned out to be a potent electrophile. Amido phospites ROP(NEt 2 ) 2 and halides R 2 X (R 2 = CC1 2 CF 3 , X= Cl; R 2 = CF=CFCF 3 , X= F; R 2 = Cfc, X= Br, I; R 2 = C(CF 3 ) 3 , X= Br; R 2 = SCF 3 , X= CF 3 ) undergo an ARBUZOV reaction.
The P(CF(3))(3)CH(3)(+) ion is synthesized as P(CF(3))(3)CH(3)(+)AsF(6)(-) by methylation in a MeF/SO(2)/AsF(5) system or as P(CF(3))(3)CH(3)(+)Sb(2)F(11)(-) in a MeF/HF/SbF(5) system at low temperatures. In contrast to (CF(3))(3)(CH(3))P(+)AsF(6)(-), P(CF(3))(3)CH(3)(+)Sb(2)F(11)(-) is a stable, colorless crystalline solid. A crystal structure determination shows the presence of a slightly distorted tetrahedral phosphonium cation with P-C(F) distances of 188.1-188.7(4) and a P-C(H) bond length of 176.7(4) pm. The phosphonium salt (CF(3))(3)(CH(3))P(+)AsF(6)(-) was also obtained by abstraction of a fluoride ion from the anion [(CF(3))(3)(CH(3))PF(2)](-) salt using AsF(5).
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