Cu(I) and Pd(II) complexes containing β-thioketoiminate ligands and their evaluation as potential redox mediators for electrochemical biosensors

Denticity governs the formation of β-thioketiminato tri-copper(i) and mono-copper(i) complexes

“…González-Ábrego et al previously reported the molecular structure of L 1 Cu(PPh 3 ) using a certain synthetic methodology. 55 In this study, we synthesized the same compound using a different procedure. The selected bond distances and angles of copper( i ) isocyanide and triphenylphosphine adducts are given in Tables S1, S2, and S3,† respectively.…”

“…previously reported the molecular structure of L 1 Cu(PPh 3 ) using a certain synthetic methodology. 55 In this study, we synthesized the same compound using a different procedure. The selected bond distances and angles of copper(I) isocyanide and triphenylphosphine adducts are given in Tables S1, S2 It is worth mentioning that there are two independent molecules of L 4 Cu(2,4,6-CNC 6 H 2 Me 3 ) in a crystallographic unit cell, which represents two binding modes depending on pyridyl arm chelation (see Fig.…”

Helical dinuclear transition metal complexes with bis(bidentate) [S,N] ligands: synthesis, structural and computational studies

“…35 The most common synthetic route to the β-thioketoimine proligands, HSacNac, is the thionation of the corresponding β-ketoimine precursors with Lawesson's reagent. 20,23,36,37 Following this precedent, conversion of H21 to H22 proceeded straightforwardly (Scheme 1), without the need for column chromatography, to afford the bis(bidentate) [N,S] proligand H22 in 40% yield. Single crystals of H22 were grown from a CH2Cl2 solution at room temperature.…”

“…Collectively these observations are consistent with a protonated βthioketoiminate tautomer (Scheme 1) as the best description of the form of H22 present in solution and the solid state, in keeping with López and co-workers description of mononucleating HSacNac Ar ; Ar = Ph, Mes and Dipp (H-3). 20,23,36,37,40 https://doi.org/10.26434/chemrxiv-2024-b25hm ORCID: https://orcid.org/0000-0002-2108-2709 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0 2)2]; M = Fe, Co and Zn, were variable (3-57%).…”

“…17, 18 Wu and co-workers employed a dinucleating ligand with two aminothiophenolate [N,S] binding domains separated by a rigid 1,3-bis(methylene)phenylene spacer to synthesise a higher-nuclear (Zn10) circular helicate. 19 There are a growing number of complexes reported with β-thioketoiminate ([SacNac] -) ligands, which have been proposed as interesting candidates for electrochemical and biological applications, [20][21][22][23] but have only recently attracted attention in catalysis. 24 Herein, we report the synthesis of an acyclic homoditopic ligand featuring two isolated [N,S] binding sites and its corresponding dinuclear complexes with first row transition metals Fe, Co and Zn.…”