Synthese und Selbstadditionsverhalten von Iminophosphanen des Typs C-P=N-C(Si)

Abstract

The synthesis and elimination reactions of aminochlorophosphanes, R-PCl-N(H,SiMe₃)R' (4a-c, 5c-i, 7b), are reported. It is shown that the iminophosphanes, R-P=N-R' (R = tBu; R' = SiMe₃, SiMe₂tBu, 2,4,6-Me₃C₆H₂) 8a, b, e are highly instable with respect to the formation of their [2 + 1]-cyclodimers 9a, b, e. The same reaction path is observed for 8d (R' = adamantyl), but at higher temperatures. In contrast, the iminophosphane intermediate 8c (R' = CH₂tBu) gives via 1,3-H-shift a diphosphane 12c. No cyclodimerisation is observed for the kinetically highly stabilized iminophosphanes 8f-i (R' = 2,4,6-tBu₃C₆H₂; R = tBu, iPr, CH(SiMe₃)₂, C₆H₅).