Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands).
Angew Chem Int Ed Engl. 2014 Aug 18;53(34):9068-71. doi: 10.1002/anie.201405027. Epub 2014 Jun 27.
Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of a novel class of 1,3-P,N ligands as demonstrated for the reaction with primary phosphanes. This procedure allows variation of all substituents. X-ray crystal structures are reported for nitrilium ions, phosphaamidines, and three phosphaamidinate complexes. The lithium phosphaamidinate is N coordinated and its reaction with [AuCl(tht)] (tht = tetrahydrothiophene) gives a unique P-bridged gold trimer, while a P,N-bidentate complex results from [{RhCl(cod)}2]. The nitrilium ion methodology allows extension of the 1,3-P,N motive to bis(imino)phosphanes, which are the neutral phosphorus analogues of the valuable β-diketiminate ligand.
易于获得的腈鎓三氟甲磺酸酯是方便的亚胺构筑块，可用于快速合成新型 1,3-P,N 配体，如与伯膦反应所示。该方法允许所有取代基的变化。报道了腈鎓离子、磷酰胺和三种磷酰胺配合物的 X 射线晶体结构。亚磷酸酰胺的锂配合物是 N 配位的，它与[AuCl(tht)]（tht =四氢噻吩）反应得到一个独特的 P 桥接金三聚体，而与[{RhCl(cod)}2]反应则得到一个 P,N-双齿配合物。腈鎓离子方法允许将 1,3-P,N 基序扩展到双(亚氨基)膦烷，其是有价值的β-二酮亚胺配体的中性磷类似物。
