Zinc Thiolate Complexes [ZnL_n(SR)]⁺ with Azamacrocyclic Ligands: Synthesis and Structural Properties

Abstract

A series of 24 novel zinc thiolate complexes containing saturated macrocyclic polyamine ligands with the general formula [Zn(L n )(SR)]ClO 4 (L n : n-dentate azamacrocyclic ligand) has been synthesized. Two different thiolate ligands (R = phenyl, benzyl) and 12 macrocyclic ligands with ring sizes varying from 11 to 16 atoms and containing three, four, and five nitrogen donors (including a new macrocyclic triamine ligand, 8-methyl-[11]aneN 3 ) have been used. The solid-state structures of 20 of the 24 complexes have been characterized by X-ray diffraction. The crystal lattice of all compounds is comprised exclusively of monomers. The tetracoordinate N 3 S compounds exhibit Zn-S bond lengths ranging from

A Triazacyclononane‐Based Bifunctional Phosphinate Ligand for the Preparation of Multimeric 68Ga Tracers for Positron Emission Tomography

“…The preparation of [9]aneN 3 followed essentially a published procedure, [45] with little alterations as described earlier. [46] NMR spectra were recorded using a UNITY Inova (400 MHz) or a VNMRS (300 MHz) spectrometer from Varian. 1 H and 13 C NMR shifts are referenced to TMS.…”

Zinc Thiolate Complexes [ZnLn(SR)]+ with Azamacrocyclic Ligands, Part III: The Influence of the Ligand Ln on the Reactivity of Zinc‐Bound Thiolate

“…Their syntheses and structures have been reported in detail before. [1] They contain 11-16-membered azamacrocycles with three (1-4) and four (5-11) secondary nitrogen donors. In three of them, namely compounds 2, 4 and 9, one tertiary nitrogen is incorporated.…”

“…Recently, we introduced a series of novel zinc thiolate complexes [1] that are ideally suited for these investigations for several reasons: 11 different compounds meeting the experimental requirements are currently available; they fea- [21] ) were found to occur cleanly and on a convenient time scale; they comprise a sufficiently small number of non-hydrogen atoms to be suited for investigation by high-level density functional calculations. The latter instance offers the possibility to reveal the effect especially of electronic parameters that are only accessible by computation, for example, orbital energies and partial charges.…”

“…Both require zinc(II) as a cofactor. Other thiol-alkylating enzymes that also feature a zinc centre in their catalytic domain are the Ada DNA repair protein, [6] farnesyl transfer- with Azamacrocyclic Ligands, Part I: Synthesis and Structural Properties [1] and energies of a lone pair in a p-type orbital at the zincbound sulfur. In order to elucidate which parameters determine reactivity, selected structural and electronic parameters were correlated with the experimental rate constants.…”

Interaction of Zinc Oxide Clusters with Molecules Related to the Sulfur Vulcanization of Polyolefins (“Rubber”)

“…This value is in good agreement with experimentally determined Zn À S bond lengths in mononuclear tetracoordinate zinc thiolate complexes (223-225 pm). [40] During the approach of the MBT molecule 19 to the ZnO cluster the initial interaction is by both an NÀH···O hydrogen bond and a C=S!Zn donor bond. On further geometry optimization the proton shifts from the nitrogen to the oxygen atom with release of substantial energy.…”