Direct Electrochemical Synthesis of an Unusual Complex Salt: Almost Structural Identity - Different Charge
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- 作者：Alexander Oppermann ; Christoph Wehrhahn ; Ulrich Flö ; rke ; Sonja Herres-Pawlis and Gerald Henkel
- 刊名：Zeitschrift für anorganische und allgemeine Chemie
- 出版年：2017
- 出版时间：February 2017
- 年：2017
- 卷：643
- 期：3
- 页码：266-275
- 全文大小：2713K
- ISSN：1521-3749
文摘
The electrochemical synthesis is an underestimated synthesis protocol, which can lead to unexpected results. We obtained an unusual Cu<sup>Isup> complex salt with a pentanuclear anion and a heptanuclear cation. The anion [Cu<sub>5sub>(StBu)<sub>6sub>]<sup>–sup> features a trigonal prism coordination motif with a twisted arrangement. The cation [Cu<sub>7sub>(StBu)<sub>6sub>(bipy)<sub>3sub>]<sup>+sup> is structurally almost identical to the anion and shares therefore basic building principles. These Cu–S skeletons with additional N donor functions in the cation have relevance to biological copper proteins. Besides structural discussion and analysis, a theoretical study was performed to determine stabilizing effects. This is accomplished by means of DFT with a triple-zeta basis set and the TPSSh functional in order to highlight bonding interactions and to understand d<sup>10sup>–d<sup>10sup> interactions, which are assigned a major stabilizing part. This is realized through Wiberg bond analysis and frontier orbital analysis of both ions.