Gas Adsorption of Mixed-Valence Trinuclear Oxothiomolybdenum Glycolates.

Trinuclear oxothiomolybdenum(IV) glycolates (Hglyc, glycolic acid) with 2-methylimidazole (2-mim), 4-methylimidazole (4-mim), and sulfite, Na[Mo(μ-S)(μ-O)(glyc)(2-mim)]·1.5HO (), (4-Hmim)[Mo(μ-S)(μ-O)(glyc)(4-mim)][MoO(glyc)] (), and Na(4-Hmim)[Mo(μ-S)(μ-O)(SO)(glyc)(4-mim)]·8HO (), have been isolated in reduced media, where 4-methylimidazole trinuclear oxothiomolybdenum(IV) glycolates in coprecipitate with dioxomolybdenum(VI) glycolate, exhibiting unusual mixed valences of 4+ and 6+. Large downfield shifts of glycolates have been observed in solid-state and solution C (H) NMR spectra with coordination to Mo, indicating obvious dissociation of soluble and in solution. Investigations of the coordination modes and conversions among the three complexes give insight into the reactivities of trinuclear oxothiomolybdenum(IV) complexes. Channels with 3.1 × 7.0 Å diameters exist in , showing reversible O absorption of 65.03 mg at 29.9 bar compared with little or no adsorption of N, H, CO, and CH at room temperature, respectively. Moreover, trinuclear 2- or 4-methylimidazole oxothiomolybdenum(IV) glycolates and show only a few adsorptions for O under the same conditions.