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Nitrogen NMR of some sulphur diimide anions and calculated (GIAO) nitrogen shielding constants
Author(s) -
Wrackmeyer Bernd,
Gerstmann Silke,
Herberhold Max,
Webb Graham A.,
Kurosu Hiromichi
Publication year - 1994
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1260320811
Subject(s) - chemistry , diimide , chemical shift , nitrogen , atomic orbital , resonance (particle physics) , ion , sulfur , electromagnetic shielding , carbon 13 nmr , crystallography , computational chemistry , analytical chemistry (journal) , stereochemistry , molecule , organic chemistry , atomic physics , physics , perylene , quantum mechanics , electrical engineering , engineering , electron
Sulphur diimide anions of the type [NSN] 2− (1), [RNSN] − (1), [R = t Bu (3), SiMe 3 (4), t Bu 2 P (5)] were prepared with the counter ions [ n Bu 4 N] + or [(Me 2 N) 3 S] + (for 1, 3, 4) and K + (for 5) and studied in solution by 14 N NMR, and for assignment purposes by 15 N NMR (4). The experimentally determined 14 N chemical shifts (δN) were compared with nitrogen shielding constants calculated by the gauge included atomic orbitals (GIAO) technique, and a linear relationship between σ N(calc) and δN was obtained. This correlation serves to support the Z configuration of the anions [RNSN] − , analogous to the isoelectronic N ‐sulphinylamines. On this basis, two 14 N resonance signals reported in the literature with uncertain assignment can be attributed to [HNSN] − (2), and the previously assigned δN values suggest that the anion [HNSNS] − (6) adopts the Z/E configuration.