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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >On mercury(I) oxo compounds - Quasi-relativistic computational and experimental studies [Review]
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On mercury(I) oxo compounds - Quasi-relativistic computational and experimental studies [Review]

机译：关于汞（I）含氧化合物-相对论计算和实验研究[评论]

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About 60 molecular species composed of up to 10 mercury atoms and of oxygen atoms and/or of some other elements or groups (such as halogen, OH2, OH, H, alkali, NO3) have been investigated quantum chemically. Different density functional approaches and the ab initio SCF-MP2 method were applied, comparing different basis sets and different atomic core sizes. It is important not to treat the Hg 5s,p,d as inactive core shells, and to use sufficiently many polarization functions. The shape of the >O-Hg-Hg-O< units is not favorable concerning the formation of lattices composed of Hg-I, 0 and OH only. Despite its bulkiness, the OHgHgO units can easily come into contact with each other and then disproportionate. This is prevented in the so-called ternary M-Hg-1 oxides by the embedded oxometallate (oxoacidic) anions. Furthermore, the Hg-I and Hg-II oxide bond energies are less favorable towards the stability of Hg-I oxo compounds, as compared to Hg halidic or oxoacidic compounds. Both points are not promising concerning the search for Hg-I oxides/hydroxides, although the preparation of such compounds, including spacer groups, by topochemical reactions can still not be excluded. So far, experimental efforts towards the synthesis of such a new class of compounds have only demonstrated that Hg-I is strictly preferred over Hg-I in the formation of solids of binary Hg-O or ternary A-Hg-O composition (A = electropositive metal such as alkali, in contrast to M = transition or semi-metal). This is so even if compounds containing 'electron rich Hgdelta- atoms' (i.e. A-Hg amalgams) are oxidized under mild conditions. [References: 108]
机译：已经通过量子化学方法研究了由多达10个汞原子和氧原子和/或某些其他元素或基团（例如卤素，OH2，OH，H，碱，NO3）组成的大约60种分子物质。应用了不同的密度泛函方法和从头算起的SCF-MP2方法，比较了不同的基集和不同的原子核尺寸。重要的是不要将Hg 5s，p，d视为非活性核壳，并使用足够多的极化函数。 > O-Hg-Hg-O <单元的形状对于仅由Hg-1、0和OH组成的晶格的形成不利。尽管体积大，但OHgHgO单元仍易于相互接触，然后成比例分布。在嵌入的金属氧酸盐（含氧酸性）阴离子中，在所谓的M-Hg-1三元氧化物中可以防止这种情况。此外，与Hg卤代或含氧酸性化合物相比，Hg-1和Hg-II氧化物键能对Hg-1含氧化合物的稳定性较不利。尽管仍不能排除通过拓扑化学反应制备此类化合物（包括间隔基）的问题，但对于寻找Hg-1氧化物/氢氧化物，这两点都没有希望。到目前为止，为合成这类新化合物而进行的实验工作仅表明，在形成二元Hg-O或三元A-Hg-O组成的固体时，Hg-I绝对优于Hg-I（A =电正性金属（例如碱），与M =过渡金属或半金属相反）。即使在温和条件下将含有“富电子的Hgdelta原子”的化合物（即A-Hg汞齐）氧化，情况也是如此。 [参考：108]

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