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在醇溶剂中合成了2个铜配合物[Cu(Ⅱ)(phen)2Br]2[Cu(Ⅰ)4Br6](1)和[Cu(Ⅱ)(phen)2Br]Br·CH3OH(2)(phen=菲咯啉),并采用红外光谱、元素分析、热重和X射线单晶衍射对其进行了分析。1是Cu(Ⅰ)-Cu(Ⅱ)混价态化合物,并通过π-π作用和C-H…Br氢键作用形成了一个超分子网络结构。该化合物的结构单元包括2个[Cu(Ⅱ)(phen)2Br]+阳离子和1个[Cu(Ⅰ)4Br6]2-四核阴离子;阴离子中的4个铜原子组成四面体结构,而6个溴原子分别沿铜四面体的6个边桥联铜原子,形成八面体结构。2由[Cu(Ⅱ)(phen)2Br]+、Br-和CH3OH组成,并通过π-π作用也形成了一个超分子网络结构。当它们催化甲醇氧化羰基化合成碳酸二甲酯(DMC)时,2仅显示了5.9的DMC转化数,而1中的[Cu(Ⅰ)4Br6]2-阴离子能为甲醇的氧化羰基化反应提供适宜的合成环境,DMC的转化数达到54.7。
Two Cu (Ⅱ) (phen) 2Br] 2 [Cu (Ⅰ) 4Br6] (1) and [Cu (Ⅱ) (phen) 2Br] Br · CH3OH phen = phenanthroline) and analyzed by IR, elemental analysis, TG and X-ray single crystal diffraction. 1 is a Cu (Ⅰ) -Cu (Ⅱ) mixed valence state compound, and a supramolecular network structure is formed by π-π interaction and C-H ... Br hydrogen bonding. The structural unit of the compound includes two [Cu (Ⅱ) (phen) 2Br] + cations and one [Cu (Ⅰ) 4Br6] 2-tetranuclear anion; four copper atoms in the anion form a tetrahedral structure, A bromine atom bridges the copper atoms along the six sides of the copper tetrahedron to form an octahedral structure. 2 is composed of [Cu (Ⅱ) (phen) 2Br] +, Br- and CH 3 OH and forms a supramolecular network structure by π-π interaction. When they catalyze the oxidative carbonylation of methanol to form dimethyl carbonate (DMC), 2 shows only 5.9 conversions of DMC, while the [Cu (I) 4Br6] 2- anion in 1 can provide for the oxidative carbonylation of methanol Appropriate synthetic environment, the number of DMC conversion reached 54.7.