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Role of the Meso Substituent in Defining the Reduction of Uranyl Dipyrrin Complexes.

ABSTRACT: The uranyl complex U^VIO₂Cl(L^Mes) of the redox-active, acyclic dipyrrin-diimine anion L^Mes- [HL^Mes = 1,9-di-tert-butyl-imine-5-(mesityl)dipyrrin] is reported, and its redox property is explored and compared with that of the previously reported U^VIO₂Cl(L^F) [HL^F = 1,9-di-tert-butyl-imine-5-(pentafluorophenyl)dipyrrin] to understand the influence of the meso substituent. Cyclic voltammetry, electron paramagnetic resonance spectroscopy, and density functional theory studies show that the alteration from an electron-withdrawing meso substituent to an electron-donating meso substituent on the dipyrrin ligand significantly modifies the stability of the products formed after reduction. For U^VIO₂Cl(L^Mes), the formation of a diamond-shaped, oxo-bridged uranyl(V) dimer, [U^VO₂(L^Mes)]₂ is seen, whereas in contrast, for U^VIO₂Cl(L^F), only ligand reduction occurs. Computational modeling of these reactions shows that while ligand reduction followed by chloride dissociation occurs in both cases, ligand-to-metal electron transfer is favorable for U^VIO₂Cl(L^Mes) only, which subsequently facilitates uranyl(V) dimerization.

SUBMITTER: van Rees K

PROVIDER: S-EPMC9768749 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

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Role of the Meso Substituent in Defining the Reduction of Uranyl Dipyrrin Complexes.

van Rees Karlotta K Rajeshkumar Thayalan T Maron Laurent L Sproules Stephen S Love Jason B JB

Inorganic chemistry 20221206 50

The uranyl complex UVIO2Cl(LMes) of the redox-active, acyclic dipyrrin-diimine anion LMes- [HLMes = 1,9-di-tert-butyl-imine-5-(mesityl)dipyrrin] is reported, and its redox property is explored and compared with that of the previously reported UVIO2Cl(LF) [HLF = 1,9-di-tert-butyl-imine-5-(pentafluorophenyl)dipyrrin] ...[more]

PMID: 36472325

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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.

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Role of the Meso Substituent in Defining the Reduction of Uranyl Dipyrrin Complexes.

Publications

Role of the Meso Substituent in Defining the Reduction of Uranyl Dipyrrin Complexes.

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