A family of octahedral rhenium cluster complexes [Re6Q8(H2O)n(OH)6-n]n-4 (Q = S, Se; n=0-6):: Structural and pH-Dependent spectroscopic studies
A family of octahedral rhenium cluster complexes [Re6Q8(H2O)n(OH)6-n]n-4 (Q = S, Se; n=0-6):: Structural and pH-Dependent spectroscopic studies
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DOI：
10.1021/ic7005265
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发表时间：
2007-09-03
影响因子：
4.6
通讯作者：
Sasaki, Yoichi
中科院分区：
文献类型：
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作者：
Brylev, Konstantin A.;Mironov, Yuri V.;Sasaki, Yoichi
采用化学方法和光谱测量方法研究了六羟基铼簇配合物[Re(6)Q(8)(OH)(6)](4-) （Q = S, Se）在宽pH范围水溶液中的转化。详细研究了溶液的光谱和激发态性质与pH的关系。研究发现，钾盐K-4[Re(6)Q(8)(OH)(6)]中心点8H(2)O （Q = S, Se）的水溶液pH值降低，可形成通式[Re(6)Q(8)(H2O)(n)(OH)(6 - n)]（n-4）的水合和六水合簇配合物，这可认为是六羟基配合物中末端OH-配体质子化的结果。对K-2[Re6S8(H2O)(2)(OH)(4)]中心点2H(2)O(1)、[Re6S8(H2O)(4)(OH)(2)]中心点12H(2)O(2)、[Re6S8(H2O)(6)][Re6S6Br8]中心点10H(2)O(3)和[Re6Se8(H2O)(4)(OH)(2)](4)化合物进行了分离和x射线单晶衍射、元素分析和红外光谱表征。在水氧配合物的晶体结构中，簇单元是通过末端配体之间非常强的氢键的广泛系统相互连接的。
The conversions of hexahydroxo rhenium cluster complexes [Re(6)Q(8)(OH)(6)](4-) (Q = S, Se) in aqueous solutions in a wide pH range were investigated by chemical methods and spectroscopic measurements. Dependences of the spectroscopic and excited-state properties of the solutions on pH have been studied in detail. It has been found that a pH decrease of aqueous solutions of the potassium salts K-4[Re(6)Q(8)(OH)(6)]center dot 8H(2)O (Q = S, Se) results in the formation of aquahydroxo and hexaaqua cluster complexes with the general formula [Re(6)Q(8)(H2O)(n)(OH)(6 - n)](n-4) that could be considered as a result of the protonation of the terminal OH- ligands in the hexahydroxo complexes. The compounds K-2[Re6S8(H2O)(2)(OH)(4)]center dot 2H(2)O (1), [Re6S8(H2O)(4)(OH)(2)]center dot 12H(2)O (2), [Re6S8(H2O)(6)][Re6S6Br8]center dot 10H(2)O (3), and [Re6Se8(H2O)(4)(OH)(2)] (4) have been isolated and characterized by X-ray single-crystal diffraction and elemental analyses and infrared (IR) spectroscopy. In crystal structures of the aquahydroxo complexes, the cluster units are connected to each other by an extensive system of very strong hydrogen bonds between terminal ligands.