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Direct Electrochemical Synthesis of an Unusual Complex Salt: Almost Structural Identity – Different Charge
Author(s) -
Oppermann Alexander,
Wehrhahn Christoph,
Flörke Ulrich,
HerresPawlis Sonja,
Henkel Gerald
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201600408
Subject(s) - electrochemistry , chemistry , ion , crystallography , salt (chemistry) , structural motif , electrode , biochemistry , organic chemistry
The electrochemical synthesis is an underestimated synthesis protocol, which can lead to unexpected results. We obtained an unusual Cu I complex salt with a pentanuclear anion and a heptanuclear cation. The anion [Cu 5 (S t Bu) 6 ] – features a trigonal prism coordination motif with a twisted arrangement. The cation [Cu 7 (S t Bu) 6 (bipy) 3 ] + 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 10 –d 10 interactions, which are assigned a major stabilizing part. This is realized through Wiberg bond analysis and frontier orbital analysis of both ions.