Remote coordination of a Ru(hfac)2 moiety to a chelating N-benzyl tetrazine lowers the C-N homolytic bond dissociation enthalpy by approximately 20 kJ mol(-1). The significant bond strength perturbation is believed to arise as a consequence of metal-ligand redox non-innocence.
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http://dx.doi.org/10.1039/c4cc06235c | DOI Listing |
Dalton Trans
January 2025
Department of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060, Nishikawatsu, Matsue, Shimane, 690-8504, Japan.
Paddlewheel-type diruthenium(II,II) complexes are paramagnetic with two unpaired electrons ( = 1) and can be utilized as versatile building blocks for higher-order structures, such as supramolecular complexes, coordination polymers, and metal-organic frameworks, although they are generally highly air-sensitive. In this study, we developed an air-stable paddlewheel-type diruthenium(II,II) complex with two electron-withdrawing 1,8-naphthyridine-2-carboxylate (npc) ligands, [Ru(μ-npc)(OCMe)] (1). The two acetate ligands in 1 can be replaced by other carboxylate ligands; the solvothermal reactions of 1 with benzoic acid (HOCPh) yields the heteroleptic [Ru(μ-npc)(OCPh)] (2), whereas its reaction with 1,8-naphthyridine-2-carboxylic acid (Hnpc) produces the homoleptic [Ru(μ-npc)(η-npc)] (3).
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, USA.
This study investigates the impact of structural isomerism on the excited state lifetime and redox energetics of heteroleptic [Ir(ppy)2(bpy)]+ and homoleptic Ir(ppy)3 photoredox catalysts using ground-state and time-dependent density functional theory methods. While the ground- and excited-state reduction potentials differ only slightly among the isomers of these complexes, our findings reveal significant variations in the radiative and non-radiative decay rates of the reactivity-controlling triplet 3MLCT states of these closely related species. The observed differences in radiative decay rates could be traced back to variations in the transition dipole moment, vertical energy gaps, and spin-orbit coupling of the isomers.
View Article and Find Full Text PDFDalton Trans
January 2025
LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, BP44099 F-31077 Toulouse cedex 4, France.
Functional pincer ligands that engage in metal-ligand cooperativity and/or are capable of redox non-innocence have found a great deal of success in catalysis. These two properties may be found in metal complexes of the 2,6-bis(pyrazol-3-yl)pyridine (bpp) ligands. With this goal in mind, we have attempted the coordination of 2,6-bis(5-trifluoromethylpyrazol-3-yl)pyridine (LCF3) and its Bu analogue 2,6-bis(5--butylpyrazol-3-yl)pyridine (LtBu) to Mo(0) by reactions with mixed phosphine/carbonyl complexes [Mo(CO)(MeCN)(PMePh)] 1-3 (1 ≤ ≤ 3).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Martin-Luther-Universitat Halle-Wittenberg, Department of Chemistry, Kurt-Mothes-Str. 2, 06120, Halle, GERMANY.
A pronounced nucleophilicity in combination with a distinct redox non-innocence is a unique feature of a coordinated ligand, which in the current case, leads to unprecedented carbon-centered reactivity patterns: A carbodiphosphorane-based (CDP) pincer-type rhodium complex allows to cleave two C-Cl-bonds of geminal dichlorides via two consecutive SN2-type oxidative additions resulting in the formation of a stabilized carbene fragment. In the presence of a suitable reductant the carbene fragment can even be converted into olefines or hydrodehalogenation products in a catalytic reaction. The developed method can also be used to convert chlorofluorocarbons (CFCs) such as CH2ClF to fluoromethane and methane.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Beijing Key Laboratory of Theory and Technology for Advanced Batteries Materials, School of Materials Science and Engineering, Peking University, Beijing 100871, P. R. China.
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