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N ‐Trimethylsilyl‐aminophosphines: Solution‐state Structures, Studied by Multinuclear Magnetic Resonance and DFT Methods
Author(s) -
Wrackmeyer Bernd,
Köhler Christian,
Weidinger Jürgen
Publication year - 2014
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201300365
Subject(s) - phosphine , trimethylsilyl , chemistry , sign (mathematics) , coupling constant , crystallography , nitrogen atom , computational chemistry , medicinal chemistry , group (periodic table) , organic chemistry , physics , mathematics , quantum mechanics , mathematical analysis , catalysis
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.