Synthesis and Structural and Spectroscopic Studies of a pH-Neutral Argentic Chelate Complex: Tribasic Silver (III) Bisperiodate.

Abstract

The preparation of stable hypervalent metal complexes containing Ag(III) has historically been challenging due to their propensity for reduction under ambient conditions. This work explores the preparation of a tripotassium silver bisperiodate complex as a tetrahydrate via chemical oxidation of the central silver atom and orthoperiodate chelation. The isolation of the chelate complex in high yield and purity was achieved via acidimetric titration. The comprehensive physiochemical characterization of the tribasic silver bisperiodate included single crystal X-ray diffraction, thermogravimetric and differential scanning calorimetry, and infrared and ultraviolet–visible spectroscopy. Infrared and UV–visible absorption spectra (λmax 255 and 365 nm) were in good agreement with historically prepared pentabasic diperiodatoargentate chelate complexes. The C2/c monoclinic distorted square planar structure of the bis-chelate complex affords a mutually supportive framework to both Ag(III) and I(VII), conferring stability under both thermal and long-term ambient conditions. Thermal analysis of the tribasic silver bisperiodate complex identified an endothermic mass loss, ΔH = +278.35 kJ/mol, observed at 139.0 °C corresponding to a solid-state reduction of silver from Ag(III) to Ag(I). Under ambient conditions, no significant degradation was observed over a 12 month period (P = 0.30) for the silver bisperiodate complex in a solid state, with an observed half-life of τ1/2 = 147 days in a pH-neutral aqueous solution.