Dataset Information

Exploring the Redox Properties of Bench-Stable Uranyl(VI) Diamido-Dipyrrin Complexes.

ABSTRACT: The uranyl complexes UO₂(OAc)(L) and UO₂Cl(L) of the redox-active, acyclic diamido-dipyrrin anion L^- are reported and their redox properties explored. Because of the inert nature of the complexes toward hydrolysis and oxidation, synthesis of both the ligands and complexes was conducted under ambient conditions. Voltammetric, electron paramagnetic resonance spectroscopy, and density functional theory studies show that one-electron chemical reduction by the reagent CoCp₂ leads to the formation of a dipyrrin radical for both complexes [Cp₂Co][UO₂(OAc)(L^•)] and [Cp₂Co][UO₂Cl(L^•)].

SUBMITTER: van Rees K

PROVIDER: S-EPMC9007458 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Exploring the Redox Properties of Bench-Stable Uranyl(VI) Diamido-Dipyrrin Complexes.

van Rees Karlotta K Hield Emma K EK Carpentier Ambre A Maron Laurent L Sproules Stephen S Love Jason B JB

Inorganic chemistry 20220207 7

The uranyl complexes UO2(OAc)(L) and UO2Cl(L) of the redox-active, acyclic diamido-dipyrrin anion L- are reported and their redox properties explored. Because of the inert nature of the complexes toward hydrolysis and oxidation, synthesis of both the ligands and complexes was conducted under ambient conditions. Voltammetric, electron paramagnetic resonance spectroscopy, and density functional theory studies show that one-electron chemi ...[more]

PMID: 35129967

Similar Datasets

Project description:A dipyrrin-supported nickel catalyst (AdFL)Ni(py) (AdFL: 1,9-di(1-adamantyl)-5-perfluorophenyldipyrrin; py: pyridine) displays productive intramolecular C-H bond amination to afford N-heterocyclic products using aliphatic azide substrates. The catalytic amination conditions are mild, requiring 0.1-2 mol% catalyst loading and operational at room temperature. The scope of C-H bond substrates was explored and benzylic, tertiary, secondary, and primary C-H bonds are successfully aminated. The amination chemoselectivity was examined using substrates featuring multiple activatable C-H bonds. Uniformly, the catalyst showcases high chemoselectivity favoring C-H bonds with lower bond dissociation energy as well as a wide range of functional group tolerance (e.g., ethers, halides, thioetheres, esters, etc.). Sequential cyclization of substrates with ester groups could be achieved, providing facile preparation of an indolizidine framework commonly found in a variety of alkaloids. The amination cyclization reaction mechanism was examined employing nuclear magnetic resonance (NMR) spectroscopy to determine the reaction kinetic profile. A large, primary intermolecular kinetic isotope effect (KIE = 31.9 ± 1.0) suggests H-atom abstraction (HAA) is the rate-determining step, indicative of H-atom tunneling being operative. The reaction rate has first order dependence in the catalyst and zeroth order in substrate, consistent with the resting state of the catalyst as the corresponding nickel iminyl radical. The presence of the nickel iminyl was determined by multinuclear NMR spectroscopy observed during catalysis. The activation parameters (ΔH‡ = 13.4 ± 0.5 kcal/mol; ΔS‡= -24.3 ± 1.7 cal/mol·K) were measured using Eyring analysis, implying a highly ordered transition state during the HAA step. The proposed mechanism of rapid iminyl formation, rate-determining HAA, and subsequent radical recombination was corroborated by intramolecular isotope labeling experiments and theoretical calculations.

Dataset Information

Exploring the Redox Properties of Bench-Stable Uranyl(VI) Diamido-Dipyrrin Complexes.

Publications

Exploring the Redox Properties of Bench-Stable Uranyl(VI) Diamido-Dipyrrin Complexes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets