Structures and spectroscopic properties of sulfur-nitrogen-pnictogen chains: R2P-N=S=N-PR2 and R2P-N=S=N-AsR2

The conformational and configurational preferences of Me2P-N=S=N-PMe2 (3) and Me2P-N=S=N -AsMe2 (4) have been identified using quantum chemical calculations at the OFT/B3LYP/6-311+G* level of theory. An approach in which energetic, structural (geometries and bond orders), electronic (analysis of the electron density) and spectroscopic properties are combined leads to the conclusion that these sulfur-nitrogen-pnictogen chains share many of the properties of their chalcogen-nitrogen analogues but that the through-space intramolecular interactions favouring the Z,Z configuration are even weaker than in these latter compounds. The results of this analysis also lead to an unambiguous assignment of the variable-temperature P-31 and N-15 NMR spectra of these compounds and their structures both in solution and in the solid state. (C) 2016 Elsevier B.V. All rights reserved.