Abstract：
Phosphoranides comprising three phosphorus carbon bonds are scarcely represented in the literature. We now utilized tris(pentafluoroethyl)phosphane, P(C2 F5 )3 , and cyanobis(pentafluoroethyl)phosphane, P(C2 F5 )2 (CN), featuring electron withdrawing pentafluoroethyl groups, to synthesize such compounds. Metal fluorides MF (M=Ag, Cs) add to P(C2 F5 )3 yielding respective M[P(C2 F5 )3 F] salts. Those M[P(C2 F5 )3 F] subsequently suffer a loss of C2 F4 , furnishing M[P(C2 F5 )2 F2 ]. The cesium salt decomposes instantaneously when warmed to rt, whereas the silver salt decomposes slowly over several days at rt. Treatment of Ag[P(C2 F5 )3 F] with 2,2\'-bipyridine facilitated the isolation and structural characterization of [Ag(bipy){P(C2 F5 )3 F}]. With P(C2 F5 )2 (CN), AgF reacts under substitution of the cyano group yielding P(C2 F5 )2 F, rather than phosphoranide formation. However, [K(18-crown-6)]F adds to P(C2 F5 )2 (CN) furnishing [K(18-crown-6)][P(C2 F5 )2 (CN)F]. Its structural characterization was successful, despite its tendency to undergo an exchange of substituents, yielding [K(18-crown-6)][P(C2 F5 )2 F2 ] and presumably [K(18-crown-6)][P(C2 F5 )2 (CN)2 ]. The latter forms an equilibrium with [K(18-crown-6)]CN and P(C2 F5 )2 (CN) which lies well on side of the phosphane and cyanide salt.
摘要：
包含三个磷碳键的磷在文献中几乎没有出现。我们现在使用三（五氟乙基）磷烷，P(C2F5)3,和氰基双(五氟乙基)磷烷，P(C2F5)2(CN),以吸电子五氟乙基为特征，合成这样的化合物。金属氟化物MF(M=Ag,Cs）添加到P（C2F5）3中，产生相应的M[P（C2F5）3F]盐。那些M[P(C2F5)3F]随后遭受C2F4的损失，提供M[P(C2F5)2F2]。当升温至室温时，铯盐瞬间分解，而银盐在rt持续数天缓慢分解。用2,2'-联吡啶处理Ag[P（C2F5）3F]促进了[Ag（bipy）{P（C2F5）3F}]的分离和结构表征。P(C2F5)2(CN)，AgF在氰基取代下反应产生P（C2F5）2F，而不是形成磷。然而,[K(18-crown-6)]F加到P(C2F5)2(CN)上,提供[K(18-crown-6)][P(C2-F5)2(CN)F]。它的结构表征是成功的，尽管它倾向于进行取代基交换，产生[K（18-冠-6）][P（C2F5）2F2]，大概[K（18-冠-6）][P（C2F5）2（CN）2]。后者与[K（18-crown-6）]CN和P（C2F5）2（CN）形成平衡，它们位于磷烷和氰化物盐的一侧。
