Direct Electrochemical Synthesis of an Unusual Complex Salt: Almost Structural Identity - Different Charge

Abstract

The electrochemical synthesis is an underestimated synthesis protocol, which can lead to unexpected results. We obtained an unusual CuI complex salt with a pentanuclear anion and a heptanuclear cation. The anion [Cu5(StBu)6]– features a trigonal prism coordination motif with a twisted arrangement. The cation [Cu7(StBu)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 d10–d10 interactions, which are assigned a major stabilizing part. This is realized through Wiberg bond analysis and frontier orbital analysis of both ions.

Copper(I) Complexes with Thiourea Derivatives as Ligands: Revealing Secrets of Their Bonding Scheme

“…Figure shows the molecular structure of the hexanuclear complex [Cu 6 (S tu N) 6 ] ( C3 ). Besides the synthetic routes described in Scheme (direct synthesis by ligand deprotonation and reaction with a copper salt or by deprotonation of C1 and C2 ), this complex could also be synthesized by electrochemical reactions with a copper plate and a platinum electrode, similarly to the reaction route of Kumar and Tuck, Kaim, or Henkel and their co‐workers.…”