P-Cyclopentadienyl-substituted 1,3,2-diazaphospholenes were prepared by salt metathesis from NaCp or LiCp* and 2-chloro-1,3,2-diazaphospholenes. Comprehensive spectroscopic and X-ray diffraction studies revealed a significant lengthening of the phosphorus–carbon bonds as compared with typical P–C bond distances, and the presence of fluxional molecular structures in solution and solid state as a consequence of circumambulatory migration of the diazaphospholene moiety around the Cp-ring. The P–C bond lengthening is accompanied by the capability to react with transition metal complexes under P–C bond activation and cyclopentadienyl transfer. At the same time, 2-Cp-diazaphospholenes react with strong bases under deprotonation to afford a phosphinyl–cyclopentadienide anion that reacts further with FeCl2 to a 1,1′-bisphosphinyl–ferrocene. The ambivalent behaviour of the diazaphospholenes offers interesting prospects to develop new synthetic methods for functional cyclopentadienyl complexes.
通过 NaCp 或 LiCp* 与 2-
氯-1,3,2-二氮
磷烯的盐析反应,制备了 P-
环戊二烯基取代的 1,3,2-二氮
磷烯。全面的光谱和 X 射线衍射研究表明,与典型的 P-C 键距离相比,
磷碳键明显延长,而且由于重氮
磷烯分子在 Cp 环周围的环状迁移,在溶液和固态中都存在通量分子结构。P-C 键延长的同时,还能在 P-C 键活化和
环戊二烯转移的作用下与过渡
金属配合物发生反应。与此同时,2-Cp-二氮杂膦烯在去质子化作用下与强碱反应,生成膦酰基-
环戊二烯阴离子,该阴离子与 FeCl2 进一步反应,生成 1,1′-
双膦酰基-
二茂铁。重氮膦烯的矛盾行为为开发功能性
环戊二烯络合物的新合成方法提供了有趣的前景。