Octahedral Co-Carbide Carbonyl Clusters Decorated by [AuPPh3]+ Fragments: Synthesis, Structural Isomerism, and Aurophilic Interactions of Co6C(CO)12(AuPPh
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- 作者：Iacopo Ciabatti ; Cristina Femoni ; Mohammad Hayatifar ; Maria Carmela Iapalucci ; Andrea Ienco ; Giuliano Longoni ; Gabriele Manca ; Stefano Zacchini
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：September 15, 2014
- 年：2014
- 卷：53
- 期：18
- 页码：9761-9770
- 全文大小：547K
- ISSN：1520-510X
文摘
The Co6C(CO)12(AuPPh3)4 carbide carbonyl cluster was obtained from the reaction of [Co6C(CO)15]2鈥?/sup> with Au(PPh3)Cl. This new species was investigated by variable-temperature 31P NMR spectroscopy, X-ray crystallography, and density functional theory methods. Three different solvates were characterized in the solid state, namely, Co6C(CO)12(AuPPh3)4 (I), Co6C(CO)12(AuPPh3)4路THF (II), and Co6C(CO)12(AuPPh3)4路4THF (III), where THF = tetrahydrofuran. These are not merely different solvates of the same neutral cluster, but they contain three different isomers of Co6C(CO)12(AuPPh3)4. The three isomers I鈥揑II possess the same octahedral [Co6C(CO)12]4鈥?/sup> carbido鈥揷arbonyl core differently decorated by four [AuPPh3]+ fragments and showing a different Au(I)路路路Au(I) connectivity. Theoretical investigations suggest that the formation in the solid state of the three isomers during crystallization is governed by packing and van der Waals forces, as well as aurophilic and weak 蟺鈥撓€ and 蟺鈥揌 interactions. In addition, the closely related cluster Co6C(CO)12(PPh3)(AuPPh3)2 was obtained from the reaction of [Co8C(CO)18]2鈥?/sup> with Au(PPh3)Cl, and two of its solvates were crystallographically characterized, namely, Co6C(CO)12(PPh3)(AuPPh3)2路toluene (IV) and Co6C(CO)12(PPh3)(AuPPh3)2路0.5toluene (V). A significant, even if minor, effect of the cocrystallized solvent molecules on the structure of the cluster was observed also in this case.