Copper(I) Thiolate Heteroadamantane Cage Structures with Relevance to Metalloproteins

Abstract

Cu–S heteroadamantanes are of great interest owing to their relevance to bioproteins. New copper(I) thiolate compounds with additional N‐donor functions from phenanthroline ligands have been synthesised. These complexes feature heteroadamantane cage structures with minor deviations in their construction and, therefore, a strong structural relationship. Furthermore, a decanuclear copper–sulfur cluster complex was isolated and shows known structural motifs arranged in a new fashion. Metallothioneins are natural counterparts to these complexes due to their thiolate‐rich and polynuclear d10 character. In addition to the structural characterisation, theoretical studies with a triple‐zeta basis set have been performed to further understand the building patterns of the reported complexes and their relevance to copper‐rich metalloproteins. This includes a Wiberg bond analysis and a full orbital analysis of selected heteroadamantanes to highlight the bonding interactions that connect the copper–sulfur skeletons.

[Cu6(NGuaS)6]2+ and its oxidized and reduced derivatives: Confining electrons on a torus

“…Compared to Cu(I)‐thiolate heteroadamantane structures one finds similar values. For comparable Cu…Cu distances, Oppermann et al calculated WBOs of around 0.11 …”

“…Furthermore, the CuN bond order is around 0.26 for a bond length of 2.1 Å. The CuS bonds conversely seem just a little bit weaker with a bond order of 0.4 for trigonal planar coordination and 0.5 for linear coordinated Cu . To understand these differences, we performed a detailed CDA analysis.…”

Detection of Copper Bisguanidine NO Adducts by UV‐vis Spectroscopy and a SuperFocus Mixer

“…Since there are still ongoing controversial discussions on whether there are Cu(I) or Cu(II) species arising and which role the nitric oxide plays in terms of oxidation states, DFT calculations and an EPR measurement of the adduct of [Cu(btmgp)Br] and NO were performed. First, a geometrical optimization was performed with the hybrid meta GGA functional TPSSh and the def2‐TZVP basis set, which proved excellent in our working group for several different cases . The Cu atom is coordinated by the two N atoms, the bromide ion, and the NO ligand in a distorted tetrahedral fashion.…”

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

“…Herein we report the direct electrochemical synthesis of an unusual complex salt with a hexanuclear cation with additional N‐donor functions and a pentanuclear anion. Both share partly identical structures, which are discussed intensively including theoretical analysis analogous to our recently published Cu–S cluster compounds …”

“…We have recently published several Cu–S cluster complexes with additional N‐donor functions and described their close similarity despite their different coordination motifs and charges . Furthermore, we identified the building principles and stabilizing forces within these scaffolds.…”