Deng Lan, Dong Xing, An Dong-Li, Weng Wei-Zheng, Zhou Zhao-Hui
State Key Laboratory for Physical Chemistry of Solid Surfaces and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Inorg Chem. 2020 Apr 6;59(7):4874-4881. doi: 10.1021/acs.inorgchem.0c00118. Epub 2020 Mar 18.
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.
三核氧硫钼（IV）乙醇酸盐（Hglyc，乙醇酸）与2 - 甲基咪唑（2 - mim）、4 - 甲基咪唑（4 - mim）和亚硫酸盐反应，得到了Na[Mo(μ - S)(μ - O)(glyc)(2 - mim)]·1.5H₂O（）、(4 - Hmim)[Mo(μ - S)(μ - O)(glyc)(4 - mim)][MoO(glyc)]（）和Na(4 - Hmim)[Mo(μ - S)(μ - O)(SO₃)(glyc)(4 - mim)]·8H₂O（），它们是在还原介质中分离得到的，其中4 - 甲基咪唑三核氧硫钼（IV）乙醇酸盐与二氧钼（VI）乙醇酸盐共沉淀，呈现出不寻常的4 +和6 +混合价态。在固态和溶液¹³C（¹H）NMR光谱中观察到乙醇酸盐与钼配位时出现大的低场位移，表明可溶性的和在溶液中明显解离。对这三种配合物的配位模式和转化的研究有助于深入了解三核氧硫钼（IV）配合物的反应活性。中存在直径为3.1×7.0 Å的通道，在29.9 bar下显示出65.03 mg的可逆O₂吸收，而在室温下分别对N₂、H₂、CO和CH₄几乎没有吸附或无吸附。此外，三核2 - 或4 - 甲基咪唑氧硫钼（IV）乙醇酸盐和在相同条件下对O₂的吸附很少。
