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.