Monomeric Fe(III)-Hydroxo and Fe(III)-Aqua Complexes Display Oxidative Asynchronous Hydrogen Atom Abstraction Reactivity.

This paper presents the synthesis and characterization of a series of novel monomeric aqua-ligated iron(III) complexes, [FeIII(L5R)(OH2)]2+ (R=OMe, H, Cl, NO2), supported by an amide-containing pentadentate N5 donor ligand, L5R [HL5R=2-(((1-methyl-1H-imidazol-2-yl)methyl)(pyridin-2-yl-methyl)amino)-N-(5-R-quinolin-8-yl)acetamide]. The complexes were characterized by various spectroscopic and analytical techniques, including electrochemistry and magnetic measurements. The Fe(III)-hydroxo complexes, [FeIII(L5R)(OH)]1+, were generated in situ by deprotonating the corresponding aqua complexes in a pH ~7 aqueous medium. In another way, adding one equivalent of a base to a methanolic solution of the Fe(III)-aqua complexes also produced the Fe(III)-hydroxo complexes. The study uses linoleic fatty acid as a substrate to explore the hydrogen atom abstraction (HAA) reactivity of both hydroxo and aqua complexes. The investigation highlights the substitution effect of the L5R ligand on reactivity, revealing a higher rate when an electron-withdrawing group is present. Hammett analyses and(or) determination of the asynchronicity factor (η) suggest an oxidative asynchronous concerted proton-electron transfer (CPET) pathway for the HAA reactions. Aqua complexes exhibited a higher asynchronicity in CPET, resulting in higher reaction rates than their hydroxo analogs. Overall, the work provides insights into the beneficial role of a higher imbalance in electron-transfer-proton-transfer (ET-PT) contributions in HAA reactivity.

Achieving Nickel Catalyzed C-S Cross-Coupling under Mild Conditions Using Metal-Ligand Cooperativity.

A simple and efficient approach of C-S cross-coupling of a wide variety of (hetero)aryl thiols and (hetero)aryl halides under mild conditions, mostly at room temperature, catalyzed by well-defined singlet diradical Ni(II) catalysts bearing redox noninnocent ligands is reported. Taking advantage of ligand centered redox events, the high-energetic Ni(0)/Ni(II) or Ni(I)/Ni(III) redox steps were avoided in the catalytic cycle. The cooperative participation of both nickel and the coordinated ligands during oxidative addition/reductive elimination steps allowed us to perform the catalytic reactions under mild conditions.

Redox-Induced Interconversion and Ligand-Centered Hemilability in NiII Complexes of Redox-Noninnocent Azo-Aromatic Pincers.

A series of nickel(II) complexes, namely, [NiII(La-c)2Cl2] (1a-c), [NiII(La,b)3](X)2 {([2a](X)2, [2b](X)2) (X = ClO4, I3)}, [NiII(Lc)2(OH2)2](ClO4)2 ([3](ClO4)2) and [NiII{(La,b)·-}2] (4a, 4b) featuring the redox-active tridentate azo-aromatic pincer ligand 2-(arylazo)-1,10-phenanthroline (L) were synthesized. The coordinated azo-aromatic ligand showed reversible hemilability depending on its formal oxidation state. On the one hand, in its native state, the unreduced ligand L shows bidentate coordination; the 1,10-phenanthroline moiety binds the central Ni(II) atom in a bidentate fashion, while the azo-chromophore remains pendent. On the other hand, the one-electron reduced ligand [L]·- binds the nickel(II) atom in a tridentate fashion. In complexes 1, [2]2+, and [3]2+, the 1,10-phenanthroline moiety of the neutral unreduced azo-aromatic ligand L binds the central nickel(II) atom in a bidentate fashion, while the azo-chromophore remains pendent. The complex 4 is a singlet diradical species, where two monoanionic azo-anion radical ligands [L]·- are bound to the central nickel(II) center in a tridentate fashion. Redox-induced reversible hemilability of the coordinated azo-aromatic ligand L was revealed from the interconversion of the synthesized complexes upon reduction and oxidation. Complex 1 upon reduction transformed to complex 4 with the loss of two chlorido ligands, whereas the complex 4 upon oxidation in the presence of excess chloride (LiCl) source transformed back to 1. Similarly, the complexes [2]2+ and 4 were also found to be interconvertible upon reduction and oxidation, respectively. Thorough experimental and density functional theory studies were performed to unveil the electronic structures of the synthesized complexes, and attempt was made to understand the redox-induced hemilability of the coordinated azo-aromatic ligand L.

Flavonol dioxygenation catalysed by cobalt(II) complexes supported with 3N(COO) and 4N donor ligands: a comparative study to assess the carboxylate effects on quercetin 2,4-dioxygenase-like reactivity.

Two new cobalt(II)-acetato complexes, [CoII(L3NCOO)(OAc)]·0.5H2O (1OAc·0.5H2O) and [CoII(L4N)(OAc)](PF6) (2OAc(PF6)), were synthesised using ligands L3NCOO- (Li+L3NCOO- = lithium 2-(benzyl((6'-methyl-[2,2'-bipyridin]-6-yl)methyl)amino)acetate) and L4N (N-benzyl-1-(6'-methyl-[2,2'-bipyridin]-6-yl)-N-(pyridin-2-ylmethyl)methanamine), respectively, to mimic the functional activity of cobalt(II)-quercetin-2,4-dioxygenase (CoII-2,4-QD). Additionally, Co(II)-flavonolato ternary complexes, [CoII(L3NCOO)(fla)]·H2O (1fla·H2O) and [CoII(L4N)(fla)](PF6) (2fla(PF6)), were synthesised as enzyme-substrate models. All four complexes were thoroughly characterised by elemental analyses and spectroscopic methods. Structural characterisation was performed for 1OAc·0.5H2O, 2OAc(PF6)·CH2Cl2 and 2fla+ with a perchlorate counter anion, 2fla(ClO4)·1.5H2O. Furthermore, density functional theory (DFT) calculations, time-dependent DFT (TD-DFT) and molecular orbital (MO) analysis were performed for the flavonolato adducts 1fla and 2fla+. The catalytic activities of complexes 1OAc·0.5H2O and 2OAc(PF6) in the oxygenative degradation of flavonol (multiple-turnover reactions) were investigated at 70 °C in DMF to determine the effect of the carboxylate substituent over a pyridyl donor residue on reactivity. Complex 1OAc·0.5H2O showed a higher catalytic rate than complex 2OAc(PF6). The same reactivity order was observed for single-turnover dioxygenation reactions with ternary complexes (1fla > 2fla+). The formation constants (Kf) of 1fla and 2fla+ species are comparable, implying that catalyst-substrate adduct formation occurs in similar amounts for both catalytic reactions. Therefore, the Kf values have a similar impact on reactivities. However, the oxidation potential of the bound fla-/fla˙ couple in 1fla is considerably lower than that in 2fla+. DFT calculations predicted that the negatively charged carboxylate group of ligand L3NCOO- determines the higher reactivity of 1fla with dioxygen by decreasing the oxidation potential of the bound fla-/fla˙ couple. During the dioxygenation process, the reactive Co(II)-bound flavonoxy radical was generated via single-electron transfer from the coordinated fla- to dioxygen, simultaneously forming a superoxide ion. The anionic carboxylate group improves the stability of the bound flavonoxy radical by providing substantial electron density to the electron-deficient fla˙ through the Co(II) centre, allowing the reactive fla˙ species to accumulate at an optimal concentration for effective catalysis. EPR spectroscopy successfully detected the cobalt-bound fla˙ species formed through the dioxygenation of 1fla. NBT2+ and EPR spin-trapping experiments confirmed superoxide formation during the dioxygenation process. So, the present work describes CoII-2,4-QD model studies and clarifies the function of carboxylate in quercetinase-like reactivity.

Probing the electronic structure of [Ru(L1)2]Z (z = 0, 1+ and 2+) (H2L1: a tridentate 2-aminophenol derivative) complexes in three ligand redox levels.

Aerobic reaction between [RuII(DMSO)4Cl2], a redox-active 2-aminophenol-based ligand (H2L1: 2-[2-(benzylthio)phenylamino]-4,6-di-tert-butylphenol) and Et3N in MeOH under refluxing conditions afforded a purple complex [Ru(L1)2] (S = 0). Structural analysis reveals that the tridentate ligand coordinates in a mer conformation providing a distorted octahedral RuN2O2S2 coordination. Cyclic voltammetry on 1 in CH2Cl2 reveals the accessability of the monocation, dication and monoanion forms. Reddish purple monocation [Ru(L1)2](PF6)·CH2Cl2 ([1OX1](PF6)·CH2Cl2; S = 1/2) and green dication [Ru(L1)2](BF4)2·H2O ([1OX2](BF4)2·H2O; S = 0) have been isolated through the chemical oxidation of 1 in CH2Cl2 by [FeIII(η5-C5H5)2](PF6) and AgBF4, respectively. A structural analysis of the single crystals of the monocation and the dication with the compositions [1OX1](PF6)·CH2Cl2·H2O (2) and [1OX2](BF4)2·1.7H2O (3), respectively, has been done. Metrical (metal-ligand and ligand backbone) parameters, values of metrical oxidation states of coordinated ligands, 1H NMR spectra of 1 and [1OX2](BF4)2·H2O, EPR spectra of [1OX1](PF6)·CH2Cl2, X-ray photoelectron and UV-VIS-NIR spectra of 1-3, spin population analysis from broken-symmetry (BS) density functional theory (DFT) calculations and quasi-restricted orbital (QRO) analysis have allowed us to assign the electronic structure of the complexes. The complexes exhibit highly covalent metal-ligand interactions. The electronic states of 1, [1OX1]1+ and [1OX2]2+ are best described as [RuII{(LISQ)˙-}2] ↔ [RuIII{(LAP)2-}{(LISQ)˙-}] (S = 0), [RuIII{(LISQ)˙-}2]1+ (S = 1/2) and [RuII{(LIBQ)0}2]2+ ↔ [RuIII{(LISQ)˙-}{(LIBQ)0}]2+ (S = 0), respectively. Notably, all redox processes are ligand-centred. Absorption spectral properties have been rationalized based on time-dependent (TD)-DFT calculations. For 1, the appearance of an IVCT band at 1100 nm supports its Class II-III (borderline) ligand-based mixed-valence character.

[CuII{(LISQ)˙-}2] (H2L: thioether-appended o-aminophenol ligand) monocation triggers change in donor site from N2O2 to N2O(2)S and valence-tautomerism.

Using a potentially tridentate o-aminophenol-based redox-active ligand H2L1 (2-[2-(benzylthio)phenylamino]-4,6-di-tert-butylphenol) in its deprotonated form, [Cu(L1)2] has been synthesized and crystallized as [CuII(L1)2]·CH2Cl2 (1·CH2Cl2). A cyclic voltammetry experiment (in CH2Cl2; V vs. SCE (saturated calomel electrode)) on 1·CH2Cl2 exhibits two oxidative (E = 0.20 V (peak-to-peak separation, ΔEp = 100 mV) and E = 0.90 V (ΔEp = 140 mV)) and two reductive (E = -0.52 V (ΔEp = 110 mV) and E = -0.92 V (ΔEp = 120 mV)) responses. Upon oxidation using a stoichiometric amount of [FeIII(η5-C5H5)2](PF6), 1·CH2Cl2 yielded [Cu(L1)2](PF6) (2). Structural analysis (100 K) reveals that 1·CH2Cl2 is a four-coordinate bis(iminosemiquinonato)copper(ii) complex (CuN2O2 coordination), and that the thioethers remain uncoordinated. The twisted geometry of 1 (distorted tetrahedral) results in considerable changes in the electronic structure, compared to well-known square-planar analogues. Crystallographic analysis of 2 both at 100 K and at 293 K reveals that it is effectively a four-coordinate complex with a CuN2OS coordination; however, a substantial interaction with the other phenolate O is observed. The metal-ligand bond distances and metric parameters associated with the o-aminophenolate rings indicate a valence-tautomeric (VT) equilibrium involving monocationic (iminosemiquinonato)(iminoquinone)copper(ii) and bis(iminoquinone)copper(i). Complex 1·CH2Cl2 is a three-spin system and a magnetic study (4-300 K) established that it has a S = 1/2 ground-state, owing to the strong antiferromagnetic coupling between the unpaired spin of the copper(ii) and the iminosemiquinonate(1-) π-radical anion. Electron paramagnetic resonance (EPR) spectral studies corroborate this result. Complex 2 is diamagnetic and the existence of VT in 2 was probed using variable-temperature (248-328 K) 1H NMR and EPR (100-298 K) spectral measurements and X-ray photoelectron spectroscopic studies at 298 K. Remarkably, modification of the well-studied 2-anilino-4,6-di-tert-butylphenol by incorporation of a benzylthioether arm leads to the occurrence of VT in 2. The electronic structure of 1·CH2Cl2 and 2 has been assigned using density functional theory (DFT) calculations at the B3LYP-D3 level of theory. Time-dependent (TD)-DFT calculations have been performed to elucidate the origin of the observed UV-VIS-NIR absorptions.