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Chelation of lanthanide and actinide cations within a suitable macrocyclic ligand often results in a rigid, kinetically inert, and thermodynamically stable complex. A benchmark for such cation-ligand suitability are cyclen-derived macrocyclic ligands, frequently used as large cation hosts for various applications. Herein, a comprehensive study of the 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane ligand (DOTAM) chelates of U IV and Ce III and their properties in aqueous solutions is presented. By employing multiple analysis techniques, including X-ray crystallography, UV-vis absorbance, 1 H NMR, UPLC-MS, cyclic voltammetry, and differential pulse voltammetry, the study has revealed that the two aqueous complexes undergo a spontaneous, gradual, and stepwise hydrolysis of each of the coordinated amides toward carboxylates. The coordination of U IV in the studied reaction has been shown to significantly enhance the reaction rate, leading to an acceleration of up to 6 orders of magnitude compared to the natural process of simple aqueous amides at room temperature. An attempt to describe the unusual chelated metal cation amide-activation feature, based on the relatively lower rigidity of the complex structure, is presented. Additionally, the electrochemical properties of the complex series are discussed in detail, along with the limitations of the analytical methods employed.

Conjugated arrays composed of corrole macrocycles are increasingly more common, but their chemistry still lags behind that of their porphyrin counterparts. Here, we report on the insertion of iron(III) into a β,β-fused corrole dimer and on the electronic effects that this redox active metal center has on the already rich coordination chemistry of [H 3 tpfc] COT, where COT = cyclo-octatetraene and tpfc = tris(pentafluorophenyl)corrole. Synthetic manipulations were performed for the isolation and full characterization of both the 5-coordinate [Fe III tpfc(py)] 2 COT and 6-coordinate [Fe III tpfc(py) 2 ] 2 COT, with one and two axial pyridine ligands per metal, respectively. X-Ray crystallography reveals a dome-shaped structure for [Fe III tpfc(py)] 2 COT and a perfectly planar geometry which (surprisingly at first) is also characterized by shorter Fe-N (corrole) and Fe-N (pyridine) distances. Computational investigations clarify that the structural phenomena are due to a change in the iron(III) spin state from intermediate ( S = 3/2) to low ( S = 1/2), and that both the 5- and 6-coordinated complexes are enthalpically favored. Yet, in contrast to iron(III) porphyrins, the formation enthalpy for the coordination of the first pyridine to Fe(III) corrole is more negative than that of the second pyridine coordination. Possible interactions between the two corrole subunits and the chelated iron ions were examined by UV-Vis spectroscopy, electrochemical techniques, and density functional theory (DFT). The large differences in the electronic spectra of the dimer relative to the monomer are concluded to be due to a reduced electronic gap, owing to the extensive electron delocalization through the fusing bridge. A cathodic sweep for the dimer discloses two redox processes, separated by 230 mV. The DFT self-consistent charge density for the neutral and cationic states (1- and 2-electron oxidized) reveals that the holes are localized on the macrocycle. A different picture emerges from the reduction process, where both the electrochemistry and the calculated charge density point toward two consecutive electron transfers with similar energetics, indicative of very weak electron communication between the two redox active iron(III) sites. The binuclear complex was determined to be a much better catalyst for the electrochemical hydrogen evolution reaction (HER) than the analogous mononuclear corrole.

The coordination and redox chemistry of aqueous Ce IV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetraacetic acid and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite-like [Ce IV 6 (O) 4 (OH) 4 (H 2 O) 8 (DOTAH) 4 ] oxo-hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in-cage complexes [Ce IV DOTP] and [Ce III DOTP(H 2 O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in-cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above-mentioned species, the in-cage [Ce IV DOTA(H 2 O)] complex structure is presented herein for the first time. An elaborative analysis of the X-ray crystallographic structural data obtained for the in-cage complexes studied herein and similar structures published previously suggests that hard-bonding cyclen-derived ligands are, counter-intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of Ln II and Ac III cations., (© 2022 Wiley-VCH GmbH.)

The Cu I/II ATP react with methyl radicals to form methane and methanol, where Cu I ATP reacts with • CH 3 in a process that is surprisingly slow. The low-rate constant of this process is attributed to the significant rearrangement of the chelating ligand required for the transient's formation. These results were corroborated by DFT calculations of the relevant compounds., (Copyright © 2022. Published by Elsevier Inc.)

The mechanism of reaction of DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) with ·CH 3 , CH 3 O 2 · and ·OH radicals were studied. The radicals were formed in situ radiolytically. The methyl radicals react orders of magnitude slower with DOTA and with M III (DOTA) - than the hydroxyl radicals. The various final products were identified and mechanisms for their formation are proposed. CH 3 O 2 · radicals do not react, or react too slowly to be observed, with DOTA and with M III (DOTA) - as long as the central cation is not oxidized by the peroxyl radical. The results imply that synthesis of the M III (DOTA) - (M III  = radioisotope) complexes in a water-organic solvent (ethanol or 2-propanol or acetonitrile) mixture is not only kinetically desired but the so formed complex also decreases the radiolytic decomposition of DOTA., (Copyright © 2022 Elsevier Inc. All rights reserved.)