Ponec Robert, Cooper David L, Savin Andreas
Institute of Chemical Process Fundamentals, Czech Academy of Sciences, Prague 6, Suchdol 2, Czech Republic.
Chemistry. 2008;14(11):3338-45. doi: 10.1002/chem.200701727.
Simple analytical models are introduced that significantly enhance the ability to understand and rationalise the nature of bonding interactions depicted by domain-averaged Fermi hole (DAFH) analysis. The examples presented show that besides shedding new light on the role of electron-sharing in ordinary two-centre two-electron (2c-2e) chemical bonds that are well represented by the classical Lewis model, the proposed approach also provides interesting new insights into the nature of bonding interactions that go beyond the traditional Lewis paradigm. This is, for example, the case of 3c-2e multicentre bonding, but a straightforward extension of the approach also reveals for direct metal-metal bonding the existence of a completely new type of bonding interaction that involves the mutual exchange of electrons between the lone pairs on adjacent metal atoms.
引入了简单的分析模型，这些模型显著增强了理解和合理化由域平均费米空穴（DAFH）分析所描绘的键合相互作用本质的能力。所举的例子表明，该方法除了能为经典刘易斯模型很好描述的普通双中心双电子（2c-2e）化学键中电子共享的作用带来新的认识外，还能为超越传统刘易斯范式的键合相互作用本质提供有趣的新见解。例如，对于3c-2e多中心键合就是如此，但该方法的直接扩展也揭示了对于直接金属-金属键合，存在一种全新类型的键合相互作用，这种相互作用涉及相邻金属原子上孤对电子之间的电子相互交换。
