Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal-CS 90032, F-67081 Strasbourg Cedex, France.
Chem Soc Rev. 2011 May;40(5):2741-60. doi: 10.1039/c0cs00102c. Epub 2011 Feb 18.
Weak attractive interactions between closed shell metal ions have been increasingly studied in the last few years and are generally designated as metallophilic interactions. They are best evidenced in the solid state where structural data obtained by X-ray diffraction provide precise information about the distance between the metals involved. The strength of such metal-metal interactions has been compared to that of hydrogen bonding (ca. 7-11 kcal mol(-1)) and is clearly sufficient to bring about novel bonding and structural features and confer interesting physical properties such as luminescence, polychromism, magnetism or one-dimensional electrical conductivity. The Cu(I)-Cu(I), Ag(I)-Ag(I) and Au(I)-Au(I) interactions have been increasingly observed and the latter have certainly been the most studied. Early qualitative analyses of the aurophilic attraction focused on Au-Au bonding originating from 6s, 6p and 5d orbital mixing. Numerous theoretical studies on metallophilic interactions continue to be carried out at various levels of sophistication which take into account relativistic and correlation effects to describe these van der Waals-type interactions. In this critical review, we would like to focus on the synthesis and structures of heterometallic clusters of the transition metals in which intra- rather than intermolecular d(10)-d(10) interactions are at work, in order to limit the role of packing effects. We wish to provide the reader with a comparative overview of the metal core structures resulting from or favoring metallophilic interactions but do not intend to provide a comprehensive coverage of the literature. We will first examine heterometallic clusters displaying homometallic and then heterometallic d(10)-d(10) interactions. Although the focus of this review is on d(10)-d(10) interactions involving metals from the group 11, we shall also briefly examine for comparison some complexes displaying intramolecular d(10)-d(10) interactions involving metals from other groups (188 references).
近年来，人们越来越多地研究闭壳层金属离子之间的弱吸引相互作用，通常将其称为金属键相互作用。在固态中，通过 X 射线衍射获得的结构数据为涉及的金属之间的距离提供了精确的信息，从而最好地证明了它们的存在。这种金属-金属相互作用的强度可与氢键（约 7-11 kcal mol(-1))相比，足以产生新颖的键合和结构特征，并赋予有趣的物理性质，如发光、多色性、磁性或一维导电性。Cu(I)-Cu(I)、Ag(I)-Ag(I) 和 Au(I)-Au(I) 相互作用已被越来越多地观察到，而后者无疑是研究最多的。早期对金键相互作用的定性分析主要集中在源自 6s、6p 和 5d 轨道混合的 Au-Au 键合上。许多关于金属键相互作用的理论研究继续在不同的复杂程度上进行，这些研究考虑相对论和相关效应来描述这些范德华型相互作用。在这篇评论中，我们希望重点关注过渡金属的杂金属簇合物的合成和结构，其中起作用的是内而非分子间的 d(10)-d(10)相互作用，以限制堆积效应的作用。我们希望为读者提供一个比较性的概述，即由于或有利于金属键相互作用而导致的金属核结构，但不打算全面涵盖文献。我们将首先检查显示同金属和然后杂金属 d(10)-d(10)相互作用的杂金属簇合物。尽管本综述的重点是涉及第 11 族金属的 d(10)-d(10)相互作用，但我们也将简要检查一些比较的复合物，这些复合物显示涉及其他族（188 个参考文献）金属的分子内 d(10)-d(10)相互作用。
