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Synthesis of Water-Soluble Planar Cobalt(II), Nickel(II), and Copper(II) Hydroxo Clusters Using a (1,4,7-Triazacyclononane)cobalt(III) Complex as a Hydrolysis-Terminating Group
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-06-24 , DOI: 10.1021/acs.inorgchem.2c01046
Sugiarto 1 , Yuya Imai 1 , Yoshihito Hayashi 1
Affiliation  

We report on a group of planar cobalt(II), nickel(II), and copper(II) hydroxo clusters that have a definite composition and are water-soluble: [{Co(tacn)(OH)2}6Co7(OH)12](NO3)2(CF3SO3)6·10H2O (1), [{Co(tacn)(OH)2}6Ni7(OH)12](NO3)2(CF3SO3)6·10H2O (2a), [{Co(tacn)(OH)2}6Ni7(OH)12](BNPP)8·6CH3NO2·8H2O [2b; BNPP = bis(p-nitrophenyl)phosphate], [{Co(tacn)(OH)2}12Ni16(OH)26(OH2)2](SO4)4(CF3SO3)10·30H2O (3a), [{Co(tacn)(OH)2}12Ni16(OH)26(OH2)2](SO4)8(CF3SO3)2·44H2O (3b), [{Co(tacn)(OH)2}2Co2(OH)2(OH2)4](SO4)(CF3SO3)2·4H2O (4), [{Co(tacn)(OH)2}2Ni2(OH)2(OH2)4](SO4)(CF3SO3)2·4H2O (5), and [{Co(tacn)(OH)2}4Cu4(OH)6](ClO4)6·5H2O (6), where tacn is 1,4,7-triazacyclononane. The peripheral of each metal hydroxo cluster plane is chemically protected by the coordination of {CoIII(tacn)(OH)2}+ groups to prevent further hydrolysis. These clusters were synthesized by the reaction of an equimolar amount of [Co(tacn)(OH2)3]3+ and cobalt, nickel, or copper salt at pH values in the range of 6.0–12.0. The structure of the cation in compounds 1, 2a or 2b, 4, and 5 is relevant to the surface structure of the cobalt phosphate and nickel borate oxygen-evolution catalysts; in particular, the Co7(OH)12 core in 1. Moreover, the arrangement of M7(OH)12 in 1 and 2a or 2b and Cu4(OH)6 in 6 represents the solid-state structures of the (111) face of the cubic CoO or NiO and the (002) plane of Cu(OH)2, respectively. Extended X-ray absorption fine structure spectra of an aqueous solution of 1, 2a, 4, and 5 exhibit well-resolved peaks at the first and second coordination spheres due to the M–O and M···M distances, respectively; the solution-state bond distances were estimated, and they agreed well with the bond distances in the solid-state structures.

中文翻译:

使用 (1,4,7-三氮杂环壬烷) 钴 (III) 配合物作为水解终止基团合成水溶性平面钴 (II)、镍 (II) 和铜 (II) 羟基簇

我们报告了一组平面钴 (II)、镍 (II) 和铜 (II) 羟基簇,它们具有确定的组成并且是水溶性的:[{Co(tacn)(OH) 2 } 6 Co 7 ( OH) 12 ](NO 3 ) 2 (CF 3 SO 3 ) 6 ·10H 2 O ( 1 ), [{Co(tacn)(OH) 2 } 6 Ni 7 (OH) 12 ](NO 3 ) 2 (CF 3 SO 3 ) 6 ·10H 2 O ( 2a ), [{Co(tacn)(OH)2 } 6 Ni 7 (OH) 12 ](BNPP) 8 ·6CH 3 NO 2 ·8H 2 O [ 2b ; BNPP = 双(硝基苯基)磷酸盐], [{Co(tacn)(OH) 2 } 12 Ni 16 (OH) 26 (OH 2 ) 2 ](SO 4 ) 4 (CF 3 SO 3 ) 10 ·30H 2 O ( 3a ), [{Co(tacn)(OH) 2 } 12 Ni 16 (OH) 26(OH 2 ) 2 ](SO 4 ) 8 (CF 3 SO 3 ) 2 ·44H 2 O ( 3b ), [{Co(tacn)(OH) 2 } 2 Co 2 (OH) 2 (OH 2 ) 4 ] (SO 4 )(CF 3 SO 3 ) 2 ·4H 2 O ( 4 ), [{Co(tacn)(OH) 2 } 2 Ni 2 (OH) 2 (OH 2 ) 4 ](SO 4)(CF 3 SO 3 ) 2 ·4H 2 O ( 5 ),和[{Co(tacn)(OH) 2 } 4 Cu 4 (OH) 6 ](ClO 4 ) 6 ·5H 2 O ( 6 ),其中tacn 是 1,4,7-三氮杂环壬烷。每个金属羟基簇平面的外围通过{Co III (tacn)(OH) 2 } +基团的配位化学保护以防止进一步水解。这些簇是由等摩尔量的[Co(tacn)(OH 2 ) 3 ] 3+反应合成的pH 值在 6.0–12.0 范围内的钴、镍或铜盐。化合物1、2a2b4、5中阳离子的结构与磷酸钴和硼酸镍氧催化剂的表面结构有关;特别是1中的 Co 7 (OH) 12核。此外,M 7 (OH) 1212a2b中的排列和 Cu 4 (OH) 66中的排列分别表示立方CoO或NiO的(111)面和Cu(OH) 2的(002)面的固态结构。由于 M-O 和 M···M 距离,1、2a、4 和 5 的水溶液的扩展 X 射线吸收精细结构光谱在第一和第二配位层处表现良好分辨估计了溶液态键距,它们与固态结构中的键距非常吻合。
更新日期:2022-06-24
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