Synthesis of mercury-linked ruthenium clusters: the X-ray structure of the new cluster dianion [{Ru6C(CO)16}2Hg]2– and the cluster [{Ru5C(CO)14(µ-Cl)}2Hg2Cl2]
Synthesis of mercury-linked ruthenium clusters: the X-ray structure of the new cluster dianion [{Ru6C(CO)16}2Hg]2– and the cluster [{Ru5C(CO)14(µ-Cl)}2Hg2Cl2]
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汞连接钌团簇的合成：新团簇双阴离子[{Ru6C(CO)16}2Hg]2–和团簇[{Ru5C(CO)14(μ-Cl)}2Hg2Cl2]的X射线结构
DOI：
10.1039/dt9910001037
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发表时间：
1991
期刊：
影响因子：
--
通讯作者：
Vijay P. Saharan
中科院分区：
文献类型：
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作者：
B. Johnson;W. Kwik;Jack Lewis;P. Raithby;Vijay P. Saharan
六钌离子[Ru6C(CO)16]2 - 1作为它的[N(PPh3)2]+盐在CH2Cl2中与等摩尔量的Hg(CF3CO2)2反应得到一种未表征的黑色聚合物，可能的分子式为[Ru6C(CO)16Hg] N。然而，在相同的溶剂中，用1等量的Hg(CF3CO2)2或2等量的HgCl2处理2等量的CH2Cl2，可以得到新的十二氢镉离子[{Ru6C(CO)16}2Hg]2 - 2。通过单晶x射线衍射分析，这种红离子被表征为[N(PPh3)2]+盐，并被证明含有两个通过汞原子连接的八面体Ru6C单元。它可能是由未表征的中间单阴离子[Ru6C(CO)16(HgX)] -3a （X = Cl或CF3CO2）产生的。与这一建议一致，化合物Hg(CF3)（CF3CO2）处理1得到单阴离子[Ru6C(CO)16(HgCF3)] -3b，该单阴离子已根据其光谱数据得到充分表征。我们还观察到中性的五砷簇[Ru5C(CO)15]4与HgCl2反应生成深红色的十砷簇[{Ru5C(CO)14（µ-Cl）}2Hg2Cl2]5。在单晶x射线衍射分析的基础上，该团簇由两个扭曲的桥蝶状Ru5C(CO)14（µ-Cl）单元组成，由一个Hg2（µ-Cl）2单元连接。在溶液中，二聚体簇5被解离成单体[Ru5C(CO)14（µ-Cl）（HgCl）]6。簇5的质谱与该单元并不完全一致，在快原子轰击质谱中，观察到与[Ru5C(CO)13（µ-Cl）（HgCl）]7相对应的离子。
Reaction of the hexaruthenium dianion [Ru6C(CO)16]2–1 as its [N(PPh3)2]+ salt in CH2Cl2 with an equimolar quantity of Hg(CF3CO2)2 leads to an uncharacterised black polymer of probable formula [Ru6C(CO)16Hg]n. However, treatment of 2 equivalents of 1 in CH2Cl2 with 1 equivalent of Hg(CF3CO2)2 or 2 equivalents of HgCl2 in the same solvent has yielded the new dodecaruthenium dianion [{Ru6C(CO)16}2Hg]2–2. This red dianion has been characterised as its [N(PPh3)2]+ salt by single-crystal X-ray diffraction analysis and shown to contain two octahedral Ru6C units linked through a mercury atom. It is probably produced from the uncharacterised intermediate monoanion [Ru6C(CO)16(HgX)]–3a(X = Cl or CF3CO2). In agreement with this suggestion, treatment of 1 with the compound Hg(CF3)(CF3CO2) yields the monoanion [Ru6C(CO)16(HgCF3)]–3b which has been fully characterised on the basis of its spectroscopic data. We have also observed that the neutral pentaruthenium cluster [Ru5C(CO)15]4 reacts with HgCl2 to produce the dark red decaruthenium species [{Ru5C(CO)14(µ-Cl)}2Hg2Cl2]5. On the basis of single-crystal X-ray diffraction analysis this cluster has been shown to consist of two distorted bridged-butterfly Ru5C(CO)14(µ-Cl) units linked by a Hg2(µ-Cl)2 unit. In solution, it appears that the dimeric cluster 5 undergoes dissociation to a monomer believed to be [Ru5C(CO)14(µ-Cl)(HgCl)]6. The mass spectrum of cluster 5 is not totally consistent with this unit and in the fast atom bombardment mass spectrum, the ion corresponding to [Ru5C(CO)13(µ-Cl)(HgCl)]7 is observed.