Building a Bridge between Coordination Compounds and Clusters: Bonding Analysis of the Icosahedral Molecules [M(ER)12] (M = Cr, Mo, W; E = Zn, Cd, Hg)
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- 作者：Moritz von Hopffgarten ; Gernot Frenking
- 刊名：Journal of Physical Chemistry A
- 出版年：2011
- 出版时间：November 17, 2011
- 年：2011
- 卷：115
- 期：45
- 页码：12758-12768
- 全文大小：1366K
- 年卷期：v.115,no.45(November 17, 2011)
- ISSN：1520-5215
文摘
The bonding situation of the icosahedral compounds [M(EH)12] (M = Cr, Mo, W; E = Zn, Cd, Hg), which are model systems for the isolated species [Mo(ZnCp*)3(ZnMe)9] possessing the coordination number 12 at the central atom M, have been analyzed with a variety of charge and energy decomposition methods (AIM, EDA-NOCV, WBI, MO). The results give a coherent picture of the electronic structure and the nature of the interatomic interactions. The compounds [M(EH)12] are transition metal complexes that possess 12 M-EH radial bond paths (AIM) that can be described as 6 three-center two-electron bonds (MO). The radial M-EH bonds come from the electron sharing interactions mainly between the singly occupied valence s and d AOs of the central atom M and the singly occupied EH valence orbitals (MO, EDA-NOCV). The orbital interactions provide 42% of the total attraction, while the electrostatic attraction contributes 58% to the metal鈥搇igand bonding (EDA-NOCV). There is a weak peripheral E鈥揈 bonding in [M(EH)12] that explains the unusually high coordination number (MO). The peripheral bonding leads for some compounds [M(EH)12] to the emergence of E鈥揈 bond paths, while in others it does not (AIM). The relative strength of the radial and peripheral bonding in [Al13]鈭?/sup> and [Pt@Pb12]2鈥?/sup> is clearly different from the situation in [M(EH)12], which supports the assignments of the former species as cluster compounds or inclusion compounds (MO, WBI). The bonding situation in [WAu12] is similar to that in [M(EH)12].