Syntheses and investigation of metal complexes with macrocyclic polythioether ligands

Abstract

Copper(I) complexes with the macrocyclic thioether ligands 1,4,8,11-tetrathiacyclotetradecane (tetrathiacyclam, 14-S4) and 1,8-dithia-4,11-diazacyclotetradecane (dithiacyclam, 14-N2S2) were synthesized and structurally characterized. While the copper(I) complexes showed no reactivity towards dioxygen, the formation...

Investigations on the Reactivity of Copper(I) Complexes with a N3S Thioether Ligand System

“…Previously, we observed that ozone could be applied to generate an end ‐ on superoxido copper complex [21] . Therefore, ozone was reacted with [Cu I ( 3 )] + in acetone at −90 °C.…”

“…Previously, we observed that ozone could be applied to generate an end-on superoxido copper complex. [21] Therefore, ozone was reacted with [Cu I (3)] + in acetone at À 90 °C. While there was an indication that a superoxido complex might have formed briefly it was not possible to really detect and character-Figure 6.…”

“…Nearly the same behavior had been observed for the reaction of [Cu(tet b)]PF 6 with dioxygen and ozone reported previously by us. [21] Unfortunately and in contrast to the quite stable copper superoxido complex with the TMG 3 tren ligand, the complex [Cu II (1)O 2 ]PF 6 started to decompose immediately after its formation and therefore, no additional experiments were performed with this system.…”

Experimental and computational investigation of heteroatom substitution in nucleolytic Cu(ii) cyclen complexes for balancing stability and redox activity

“…Older and recent examples of macrocyclic ligands with different heteroatoms have focused on the larger analog cyclam (1,4,8,11-tetraazatetradecane), e.g. the Cu(I) and Cu(II) complexes of the trans-dithiacyclam derivative have been suggested as analogs of blue copper proteins and copper monooxygenases, [17][18][19] and its Cu(II) complex with two molecules of diclofenac, a nonsteroidal anti-inflammatory drug (NSAID) at the axial positions, has been used to generate reactive oxygen species (ROS) for killing breast cancer cells and highly resistant breast cancer stem cells. 20 In the last couple of years, we have systematically investigated the coordination chemistry and electrochemical properties of Cu(II) cyclen derivatives substituted with one sulfur or one and more oxygen donors.…”

Template Synthesis (Self-Assembly) of Macrocycles: Theory and Practice

“…Particularly interesting in the reactions of “self-assembly” are the so-called ambidentate, primarily (N,O,S,P)-donor atomic ligand synthons, which, depending on the starting conditions for the complexation and the nature of the metal ion, are capable of being coordinated to the latter by means of various donor atoms. The given circumstance, on the one hand, opens up new opportunities for the targeted synthesis of a wide variety of metal macrocyclic compounds and, on the other hand, in some cases, makes it possible to obtain new, previously unknown metal complexes; this is undoubtedly valuable for both fundamental and applied coordination and supramolecular chemistry (see the articles [ 12 , 13 , 14 , 15 , 16 , 17 ] for further information).…”