Synthesis and structures of [S(H)P(μ-NR)]2, potential building blocks for inorganic phosphorus–sulfur macrocycles

Abstract

The reactions of the chloro-phosph(III)azane dimers [ClP(μ-NR)]₂ with LiSH give the dimers [S(H)P(μ-NR)]₂ (III), which are potential new building blocks for inorganic macrocycles of the type [{P(μ-NR)}₂(μ-S)]_n. NMR spectroscopic studies and DFT calculations show that the preference for the cis or trans isomers of III is largely influenced by the steric demands of the R-group, with cis isomers being preferred for bulky substituents. This is an important factor in regard to applications in macrocycle synthesis since the cis arrangement is pre-organized for cyclisation.