On thio‐substituted N‐heterocyclic arsines

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.