Quaternization and oxidation reactions of cyclodiphosphazane derivatives and their copper(I) and gold(I) complexes.

Abstract

Three cyclodiphosphazane derivatives were reacted with methyl iodide and methyl triflate, yielding selectively quaternized products at phosphorus or exocyclic nitrogen atoms depending on the substrate. Subsequent reactions with elemental sulfur or selenium produced cis/trans chalcogenide mixtures as well as mono- and bischalcogenide species. Coordination with CuI afforded dinuclear complexes and a coordination polymer featuring triiodo-bridged Cu2(μ-I)3 units. The Cu(I)···Cu(I) separation of 2.55 Å in one complex matches that of bulk copper metal. Single-crystal X-ray diffraction confirmed the molecular structures, and all metal complexes displayed intra- and/or intermolecular hydrogen bonding interactions.