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 NMR spectroscopic studies revealed that a thiocyanato-diazarsolene exhibits salt-like structure composed weakly interacting thiocyanate arsenium ions, while the remaining products formed neutral molecules. The structural data indicate heterocyclic framework induces an elongation exocyclic As−S bonds is more prominent in diazarsolenes than diazarsolidines parallels bond polarisation effect established for phosphines. suggest undergo facile inversion pyramidal configuration at arsenic, which was successfully modelled by DFT studies.