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 2 J ( 31 P,N, 13 C) and 2 J ( 31 P,N, 29 Si), known to be sensitive towards the respective conformation, are well reproduced by the calculations. This also holds for 1 J ( 31 P, 15 N), although calculated values 1 K ( 31 P, 15 N) (all < 0) are slightly more negative [ 1 J ( 31 P, 15 N) more positive] than experimental values.