Systematic build-up of high-nuclearity osmium–mercury clusters
Systematic build-up of high-nuclearity osmium–mercury clusters
复制标题
高核锇汞簇的系统构建
DOI：
10.1039/dt9920000921
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发表时间：
1992
期刊：
影响因子：
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通讯作者：
H. Powell
中科院分区：
文献类型：
--
作者：
L. Gade;B. Johnson;Jack Lewis;M. Mcpartlin;H. Powell
研究了簇状双阴离子[Os10C(CO)24]2-1作为底物与汞(II)的氧化还原缩合反应。它与HgX2(X=氯、溴或碘)反应，首先生成卤化汞簇合物[Os10C(CO)24(HgX)]-(X=Cl2a、Br2b或I2c)，在溶液中发生再分配反应。这可以通过用CF3基团封闭汞原子的一个配位位置来防止，从而产生稳定的单阴离子[Os10C(CO)24(HgCF3)]-2d。通过单晶X-射线结构分析确定了2b的[N(PPh3)2]+盐和2d的[PPh4]+盐的结构。1与0.5~0.7当量的Hg(O_3SCF_3)_2反应，选择性地生成了含汞的簇状二阴离子[{Os10C(CO)_(24)_2HG]_2，其结构经X射线单晶测定为[N(PPh_3)_2]+盐。这一综合概念的极限是由团簇的氧化还原行为决定的。用1实现的团簇建立与它的四氢类似物[Os10H4(CO)24]2-不发生，相反，它被汞盐氧化产生自由基单阴离子。
The cluster dianion [Os10C(CO)24]2–1 has been studied as a substrate for redox condensations with mercury(II) electrophiles. Its reaction with HgX2(X = Cl, Br or I) initially generates the halogenomercury-capped clusters [Os10C(CO)24(HgX)]–(X = Cl 2a, Br 2b or I 2c) which undergo redistribution reactions in solution. This can be prevented by blocking one co-ordination site of the Hg atom with a CF3 group, thus producing the stable monoanion [Os10C(CO)24(HgCF3)]–2d. The structures of the [N(PPh3)2]+ salt of 2b and the [PPh4]+ salt of 2d were established by single-crystal X-ray structure analysis. The reaction of 1 with 0.5–0.7 equivalent of Hg(O3SCF3)2 leads to selective formation of the Hg-linked cluster dianion [{Os10C(CO)24}2Hg]2– the structure of which was determined by X-ray crystallography as its [N(PPh3)2]+ salt. The limits of this synthetic concept are set by the redox behaviour of the cluster. The cluster build-up achieved with 1 does not take place with its tetrahydrido analogue [Os10H4(CO)24]2–, which is instead oxidised by mercury salts to yield the radical monoanion.