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On thio‐substituted N‐heterocyclic arsines
Author(s) -
Bender Johannes,
Skowrońska Agnieszka,
Dołęga Anna,
Nieger Martin,
Gudat Dietrich
Publication year - 2021
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.202100006
Subject(s) - chemistry , thiocyanate , thio , nucleophile , metathesis , sulfur , molecule , salt metathesis reaction , stereochemistry , sn2 reaction , crystallography , medicinal chemistry , organic chemistry , catalysis , polymer , polymerization
Metathesis of N‐heterocyclic chloroarsines with sulfur‐based nucleophiles furnished thio‐substituted 1,3,2‐diazarsolidines and 1,3,2‐diazarsolenes. Crystallographic and NMR spectroscopic studies revealed that a thiocyanato‐diazarsolene exhibits a salt‐like structure composed of weakly interacting thiocyanate and arsenium ions, while the remaining products formed neutral molecules. The structural data indicate that the heterocyclic framework induces an elongation of exocyclic As−S bonds that is more prominent in diazarsolenes than in diazarsolidines and parallels the bond polarisation effect established for N‐heterocyclic phosphines. The NMR data suggest that diazarsolenes undergo facile inversion of the pyramidal configuration at arsenic, which was successfully modelled by DFT studies.