Zhang Xinxing, Bowen Kit
Departments of Chemistry and Material Sciences, Johns Hopkins University, Baltimore, Maryland, MD, 21218, USA.
Chemistry. 2017 Apr 24;23(23):5439-5442. doi: 10.1002/chem.201701067. Epub 2017 Mar 29.
Being electrostatic interactions in nature, hydrogen bonding (HB) and halogen bonding (XB) are considered to be two parallel worlds. In principle, all the applications that HB have could also be applied to XB. However, there has been no report on an anionic, metallic XB acceptor, but metal anions have been observed to be good HB acceptors. This missing mosaic piece of XB theory is because common metal anions are reactive for XB donors. In view of this, two strategies are proposed for designing metallic acceptor-containing XB using ab initio calculations. The first one is to utilize a metal cluster anion with a high electron detachment energy, such as the superatom, Al as the XB acceptor. The second strategy is to design a ligand-passivated/protected metal core that can maintain the negative charge; several exotic clusters, such as PtH , PtZnH , and PtMgH , are used as examples. Based on these two strategies, it is anticipated that more metallic acceptor-containing XBs will be discovered.
氢键（HB）和卤键（XB）本质上是静电相互作用，被认为是两个平行的领域。原则上，所有HB能应用的领域也都可以应用于XB。然而，目前尚未有关于阴离子型金属XB受体的报道，不过金属阴离子已被观察到是良好的HB受体。XB理论中这一缺失的部分是因为常见的金属阴离子对XB供体具有反应性。有鉴于此，利用从头算计算提出了两种设计含金属受体的XB的策略。第一种是利用具有高电子脱离能的金属簇阴离子，如超原子Al作为XB受体。第二种策略是设计一种能保持负电荷的配体钝化/保护的金属核；以几种奇特的簇合物，如PtH、PtZnH和PtMgH为例。基于这两种策略，预计将会发现更多含金属受体的XB。
