Dative Bonds in Main-Group Compounds: A Case for Fewer Arrows!
Dative Bonds in Main-Group Compounds: A Case for Fewer Arrows!
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DOI：
10.1002/anie.201300461
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发表时间：
2014-01-07
影响因子：
16.6
通讯作者：
Schnepf, Andreas
中科院分区：
文献类型：
--
作者：
Himmel, Daniel;Krossing, Ingo;Schnepf, Andreas
近年来债券箭头“！”在主族化合物的结构式中越来越频繁地使用。[1, 2] 由此，Alfred Werner 100年前引入的中心原子和配体的术语从过渡金属化学转移到了主族元素。例如，中性化合物 L2Si2 [L= N-杂环卡宾] 被讨论为 SiO 化合物 [3]，并在《科学》杂志上同时发表的 Perspectives 文章中将其描述为硅的新“可溶同素异形体”（图 1）。[4]按照此命名法，卡宾配体的影响应该相当小，考虑到计算出的 SiÀC 键能为 169 kJmolÀ1，这是值得怀疑的。类似地，例如，[Fe2 (CO) 9] 和 [Fe3 (CO) 12] 同样可以被声明为铁的可溶同素异形体。尽管如此，使用配位键对 L2Si2 的描述似乎仍然是合适的，尽管作为双两性离子的公式强调与同瓣二磷菲的关系（图 1），肯定具有相似的重量，并且有助于直接理解其电子结构。
In recent years bond arrows “!” have been used more and more frequently in the structural formulae of main-group compounds.[1, 2] Thereby, the terminology of a central atom and ligand as introduced by Alfred Werner 100 years ago is transferred from transition-metal chemistry to the maingroup elements. For example, the neutral compound L2Si2 [L= N-heterocyclic carbene] was discussed as a Si0 compound [3] and described as a new “soluble allotrope” of silicon in a simultaneously published Perspectives article in Science (Figure 1).[4]Following this nomenclature the influence of the carbene ligand should be rather small, which is doubtful considering the calculated SiÀC bond energy of 169 kJmolÀ1. Similarly [Fe2 (CO) 9] and [Fe3 (CO) 12], for example, could equally well be declared as soluble allotropes of iron. Nevertheless, the description of L2Si2 using dative bonds still seems to be appropriate, although the formulation as double zwitterion, which emphasizes the relation to the isolobal diphosphenes (Figure 1), would certainly have a similar weight and would have been helpful for the straightforward understanding of its electronic structure.