Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu鈥?H)B Interaction in [Cu2(bipy)2B10H10]

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• 作者：Anna V. Vologzhanina ; Alexander A. Korlyukov ; Varvara V. Avdeeva ; Irina N. Polyakova ; Elena A. Malinina ; Nikolai T. Kuznetsov
• 刊名：Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：December 12, 2013
• 年：2013
• 卷：117
• 期：49
• 页码：13138-13150
• 全文大小：686K
• 年卷期：v.117,no.49(December 12, 2013)
• ISSN：1520-5215

文摘

Interaction of [Cu₂B₁₀H₁₀] with 2,2鈥?bipyridine (bipy) afforded a novel binuclear discrete complex of the [Cu₂(bipy)₂B₁₀H₁₀] composition. Two copper(I) atoms coordinate a bridge boron cage through an apical edge and a triangular BBB face situated at its opposite apical vertices to form four 3c2e (CuHB) and one 2c2e Cu鈥揃 bonds. The charge density model was obtained by density functional theory calculations of isolated molecule and crystal. The resultant densities were analyzed using the quantum theory of atoms in molecules (QTAIM) and electron localizability indicator (ELI-D). The geometry and the topological parameters of copper(I) coordination environment were found to be sensitive to crystal-field effect. An annulus of flat electron density 蟻(r) and small ²蟻(r) is formed at dianion faces. As a result, some of the expected B鈥揃, Cu鈥揃, or Cu鈥揌 bond critical points are absent. The topological instability in the region of multicentered bonds is observed. The Cu鈥揃 bonding was found to be presumably electrostatic in nature, which could be the reason of topological isomerism for copper(I) decaborates. The results show that an unambiguous real-space criterion for multicentered bonding between transition metals and polyhedral boron anions is not yet given. The molecular graph for this class of compounds does not provide a definitive picture of the chemical boding and can be complemented with other descriptors, such as virial graphs and the ELI-D distribution.