N-Trimethylsilyl-aminophosphines: Solution-state Structures, Studied by Multinuclear Magnetic Resonance and DFT Methods

A novel fairly stable N‐trimethylsilylamino(dichloro)phosphine was prepared, in which the nitrogen atom bears a 9‐borabicyclo[3.3.1]nonyl group. The gas phase structures of various amino‐ and silylaminophosphines including a phosphenium cation and an amino(imono)phosphine were optimized at the B3LYP/6‐311+G(d,p) level of theory, and NMR parameters were calculated. Both magnitude and sign of the two‐bond coupling constants 2J(31P,N,13C) and 2J(31P,N,29Si), known to be sensitive towards the respective conformation, are well reproduced by the calculations. This also holds for 1J(31P,15N), although calculated values 1K(31P,15N) (all < 0) are slightly more negative [1J(31P,15N) more positive] than experimental values.