Triorganylphosphoranides: Realization of an Unusual Structural Motif Utilizing Electron Withdrawing Pentafluoroethyl Groups
作者:Mira Keßler、Michael Kapiza、Hans‐Georg Stammler、Beate Neumann、Gerd‐Volker Röschenthaler、Berthold Hoge
DOI:10.1002/cplu.202200436
日期:——
Fluoride addition to P(C2F5)3 and P(C2F5)2(CN) furnished respective [P(C2F5)3F]− and [P(C2F5)2(CN)F]− salts, featuring the unusual structural motif of small, open-chained phosphoranides with three phosphorus carbon bonds. This work reports upon the formation and decomposition of Cs[P(C2F5)3F] and Ag[P(C2F5)3F], the solid-state structures of [Ag(bipy)P(C2F5)3F}] and [K(18-crown-6)][P(C2F5)2(CN)F],
包含三个磷碳键的磷腈在文献中几乎没有出现。我们现在利用三(五氟乙基)膦 P(C2F5)3 和氰基双(五氟乙基)膦 P(C2F5)2(CN),具有吸电子五氟乙基基团,来合成此类化合物。金属氟化物 MF(M = Ag、Cs)添加到 P(C2F5)3 中,生成相应的 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]。铯盐在加热到室温时会立即分解,而银盐在室温下会在几天内缓慢分解。用 2,2'-联吡啶处理 Ag[P(C2F5)3F] 有助于 [Ag(bipy)P(C2F5)3F}] 的分离和结构表征。对于 P(C2F5)2(CN),AgF 在氰基取代的情况下发生反应,生成 P(C2F5)2F,而不是形成磷化物。然而,[K(18-crown-6)]F 添加到 P(C2F5)2(CN) 提供 [K(18-crown-6)][P