Organomercury-based imino-bis(diisopropylphosphine chalcogenide) complexes: synthesis and characterisation of novel hybrid “single-source precursors” for mercury chalcogenide solid-state materials

Abstract

The synthesis and characterisation of the mercury(II) complexes [RHg{(SePⁱPr₂)₂N}] [R = methyl (2a), ethyl (3a), thienyl (T) (4a), 2-selenyl (SL) (5a) and phenyl (6a)], prepared by the reaction of the sodium salt of NH(SePⁱPr₂)₂ (1a) with the appropriate alkyl/aryl mercury halide in methanol are reported. Results are compared and contrasted to the corresponding sulfur analogues [RHg{(SPⁱPr₂)₂N}] [R = T (4b), SL (5b) and Ph (6b)], and these new compounds have been evaluated, by thermogravimetric analysis and mass spectrometry as potential precursors and powder X-ray diffraction used to identify solid-state products. The solid-state structure of the symmetrical complex Hg[(SePⁱPr₂)₂N]₂7a, and di(2-selenyl)mercury, one of the symmetrisation products of [SLHg{(SePⁱPr₂)₂N}] 5a in solution, have been determined by single crystal X-ray crystallography.