Redox-active Ligand Research Articles

An ancillary-ligand strategy for the improvement of electrochemical sensing towards S-containing amines with ultralow detection limits

A Zn-MOF electrochemical sensor was synthesized using an “ancillary-ligand strategy”. With the introduction of redox-active ancillary ligand azpy and the host–guest interactions, the sensor exhibits an ultralow detection limit for l-methionine.

Synthesis and electrochemical properties of molybdenum nitrido complexes supported by redox-active NHC and MIC ligands

We report the synthesis of a series of molybdenum nitrido complexes supported by bis-phenolate N-heterocyclic and mesoionic carbenes, to investigate their (electro-)chemical properties in the absence and presence of protons for ammonia production.

Mechanisms of hydrogen evolution by six-coordinate cobalt complexes: a density functional study on the role of a redox-active pyridinyl-substituted diaminotriazine benzamidine ligand as a proton relay.

The hydrogen evolution reaction is an important process for energy storage. The six-coordinate cobalt complex [CoIII(L1-)(LH)]2+ (LH = N-(4-amino-6-(pyridin-2-yl)-1,3,5-triazin-2-yl)benzamidine) was found to catalyze photocatalytic hydrogen evolution. In this work, we performed density functional calculations to obtain the reduction potentials and the proton-transfer free energy of possible intermediates to determine the preferred pathways for proton reduction. The mechanism involves the metal-based reduction of Co(III) to Co(II) before the protonation at the amidinate N on the pyridinyl-substituted diaminotriazine benzamidinate ligand L1- to form [CoII(LH)(LH)]2+. Essentially, the subsequent electron transfer is not metal-based reduction, but rather ligand-based reduction to form [CoII(LH)(LH˙1-)]1+. Through a proton-coupled electron transfer process, the cobalt hydride [CoIIH(LH)(LH2˙)]1+ is formed as the key intermediate for hydrogen evolution. As the cobalt hydride complex is coordinatively saturated, a structural change is required when the hydride on Co is coupled with the proton on pyridine. Notably, the redox-active nature of the ligand results in the low acidity of the protonated pyridine moiety of LH2˙, which impedes its function as a proton relay. Our findings suggest that separating the proton relay fragment from the electron reservoir fragment of the redox-active ligand is preferred for fully utilizing both features in catalytic H2 evolution.

Ni(II) and Pd(II) complexes of a new redox-active pentadentate azo-appended 2-aminophenol ligand: Pd(II)-assisted intraligand cyclization forms a phenoxazinyl ring.

Square planar complexes of Ni(II) and Pd(II) of a new redox-active pentadentate azo-appended 2-aminophenol ligand (H4L = N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)-2,2'-diamino-ortho-azobenzene) in three accessible redox levels [amidophenolate(2-), semiquinonate(1-) π radical, and quinone(0)] were synthesized. The coordinated HL(3-) ligand provides four donor sites [two N(iminophenolates), an N'(azo), and an O(phenolate)], while the phenolic OH group remains free in the three complexes. Cyclic voltammetry on complex [Ni(L)] 1 and its corresponding Pd(II) analogue [Pd(L)] 2 in CH2Cl2 displayed three redox responses (two oxidative at E1/2 = 0.06 V and Epa (anodic peak potential) = 0.80 V and one reductive at -0.77 V for 1 and at E1/2 = 0.08 V and Epa = 0.85 V and at -0.74 V for 2vs. Fc+/Fc). The chemical oxidation of 1 with AgSbF6 afforded [Ni(L)]SbF6·2CH2Cl2 (3·2CH2Cl2). Complex [Pd(L*)] 4, which is coordinated by a phenoxazinyl derivative of L(4-), was obtained via intraligand cyclization in the parent complex 2 under basic oxidizing conditions. The molecular structures of 1, 2, 3·2CH2Cl2 and 4 were elucidated through X-ray crystallography at 100 K. Characterization using 1H NMR, X-band EPR, and UV-VIS-NIR spectroscopy established that the complexes have [NiII{(LISQ)˙2-}] 1, [PdII{(LISQ)˙2-}] 2, [NiII{(LIBQ)-}]SbF6/1+SbF6-(3), and [PdII{(L*AP)˙2-}] 4 electronic states. Complexes 1, 2, and 4 possess paramagnetic St (total spin) = 1/2 ground-state, whereas 3 is diamagnetic (St = 0). Density functional theory (DFT) electronic structural calculations at the B3LYP level rationalized the observed experimental results. Time-dependent (TD)-DFT calculations allowed us to identify the nature of the observed absorption spectra.

A redox-active ligand combines a PCP pincer site with a bidentate N–N donor in opposition

A binucleating ligand (2) combining a monoanionic PCP pincer cleft with a monoanionic N–N cleft has been prepared on the basis of bis(imidazolyl)methane (1).

Unveiling the Anomaly of Reduction of Carborane-bis-silylene-Stabilised Silylone/Germylone Leading to Unusual Oxidation of Si0 /Ge0 to SiI /GeI with EDA-NOCV Analyses.

Researchers have successfully isolated Si0 /Ge0 species, termed silylone and germylone, with two lone pairs of electrons on them. These elusive compounds have been stabilised in singlet ground states by using different donor base ligands. Driess et al. in particular have made strides in this area, isolating carborane-bis-silylene-stabilised silylone/germylone and their N+ /Pb analogues. Carborane (C2 B10 H10 ) plays a pivotal role as a redox-active ligand, converting from closo-carborane to nido-carborane with the addition of two electrons. Notably, anomalous oxidation of Si0 /Ge0 centres in carborane-bis-silylene-stabilised species to SiI /GeI has been reported, resulting in the formation of dimeric SiI -SiI /GeI -GeI di-cationic units. The energy decomposition analysis coupled with natural orbital for chemical valence (EDA-NOCV) study focuses on the carborane-bis-silylene ligand in the free state, and its three other species, including silylone/germylone species. Interestingly, it reveals that the carborane unit in an anionic doublet state tends to form one electron-sharing bond and one dative bond with the counter fragment in its cationic doublet state. This helps us to rationalise why the carborane unit undergoes intramolecular electronic rearrangements leading to the formation of a di-anionic carborane unit with a significantly elongated C-C bond (2.38-2.68 Å) and undergoes unusual oxidation of Si0 /Ge0 to SiI /GeI .

Modulation of the Bonding between Copper and a Redox-Active Ligand by Hydrogen Bonds and Its Effect on Electronic Coupling and Spin States.

The exchange coupling of electron spins can strongly influence the properties of chemical species. The regulation of this type of electronic coupling has been explored within complexes that have multiple metal ions but to a lesser extent in complexes that pair a redox-active ligand with a single metal ion. To bridge this gap, we investigated the interplay among the structural and magnetic properties of mononuclear Cu complexes and exchange coupling between a Cu center and a redox-active ligand over three oxidation states. The computational analysis of the structural properties established a relationship between the complexes' magnetic properties and a bonding interaction involving a dx2-y2 orbital of the Cu ion and π orbital of the redox-active ligand that are close in energy. The additional bonding interaction affects the geometry around the Cu center and was found to be influenced by intramolecular H-bonds introduced by the external ligands. The ability to synthetically tune the d-π interactions using H-bonds illustrates a new type of control over the structural and magnetic properties of metal complexes.

Non-Metals Chelated by Redox Active Chelators as Electrocatalysts for Hydrogen Evolution Reaction (HER)

Global energy needs the development of non-polluting and renewable sources. Hydrogen is most attractive as such, it has high energy density of 140 MJ/Kj and water as a byproduct.1 Despite the “simplicity” of the H-H bond, a catalyst is required to make its formation process efficient and economic.2 Although platinum group metal (PGM) are the best catalysts for the Hydrogen Evolution Reaction (HER) to date, they are rare and expensive.3 Conventional HER catalysis employs a transition metal with the ability to accommodate several oxidation states for the two-electron hydride transfer associated with hydrogen evolution. Emerging interest is being shown in the utilization of redox-active ligands that open alternative HER pathways, such as ligand-assisted metal-centered,4 ligand-centered,5and metal-assisted ligand-centered reactivity.6 Antimony corroles7 and two boron subphthalocyanines8 are reported as HER electrocatalysts. For that, two new corroles with electron donating and electron withdrawing meso-substituents were fully characterized X-ray crystallography, NMR, electronic spectra, and electrochemistry. All the complexes were studied under homogeneous conditions (CH3CN solvent and TFA as proton source), which revealed that catalysis relies on ligand reduction, in contrast with ordinary transition metal complexes. It revealed that the electron withdrawing substituents are best for homogeneous catalysis and the most electron rich substituents are best in heterogeneous catalysis in terms of onset potential and faradaic efficiency due to secondary sphere.

Metal-Ligand Redox Cooperativity in Cerium Amine-/Amido-Phenolate-Type Complexes.

The synthesis and characterization of two cerium complexes of redox-active amine/amido-phenolate-type ligands are reported. A tripodal framework comprising the tris(2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)amino-phenyl) amine (H6Clamp) proligand was synthesized for comparison of its cerium complex with a potassium-cerium heterobimetallic complex of the 4,6-di-tert-butyl-2-[(2,6-diisopropylphenyl)imino]quinone (dippap) proligand. Structural studies indicate differences in the cerium(III) cation coordination spheres, where CeIII(CH3CN)1.5(H3Clamp) (1-Ce(H3Clamp)) exhibits shorter Ce-O distances and longer Ce-N bond distances compared to the analogous distances in K3(THF)3CeIII(dippap)3 (2-Ce(ap)), due to the gross structural differences between the systems. Differences are also evident in the temperature-dependent magnetic properties, where smaller χT products were observed for 2-Ce(ap) compared to 1-Ce(H3Clamp). Solution electrochemical studies for the complexes were interpreted based on ligand- and metal-based oxidation events, and the cerium(III) oxidation of 2-Ce(ap) was observed to be more facile than that of 1-Ce(H3Clamp), behavior that was cautiously attributed to the rigidity of the encrypted 1-Ce(H3Clamp) complex compared to the heterobimetallic framework of 2-Ce(ap). These results contribute to the understanding of how ligand designs can promote facile redox cycling for cerium complexes of redox-active ligands, given the large contraction of cerium-ligand bonds upon oxidation.

Cooperation between p-Block Elements and Redox-Active Ligands: Stoichiometric and Catalytic Transformations.

The relevance acquired by redox-active ligands in modern catalysis stems from their facile delivery and acceptance of electrons, either to the metal they coordinate to, or directly to an incoming substrate that also binds the central metal. Doing that, they generate coordinated radicals and provide access to more than one spin state during the catalytic cycle. As a consequence, the new reaction barriers are reduced when compared to similar processes that are restricted to a single spin surface. The principles that govern this genuine approach to catalyst design are well-established, and their implementation has allowed the development of synthetically useful catalytic transformations; however, the extension of the concept to species in which p-block elements take the role of central atoms remains largely underdeveloped. Through discussion of the key achievements and recent progress, this Concept Article highlights this original approach to designing (organo)catalysts, discloses the progress achieved, and also reveals the many shortcomings that still exist in the field.

Metal Complexes with Redox-Active Ligands in the Indirect Electrosynthesis of Organic Sulfur Compounds

Metal Complexes with Redox-Active Ligands in the Indirect Electrosynthesis of Organic Sulfur Compounds

Electron-Triggered Imine Coupling: Synthesis and Characterization of Three Redox States (0,-1,-2) of a Ni(N2 S2 ) Complex.

Metal imine-thiolate complexes, M(NS)2 are known to undergo imine C-C bond formation to give M(N2 S2 ) complexes (M=Co, Ni) containing a redox-active ligand. Although these transfor-mations are not typically quantitative, we demonstrate here that the one-electron reduction of a related Ni bis(imine-thiolate) complex affords the corresponding paramagnetic [Ni(N2 S2 )]- anion (2⋅- ) exclusively; subsequent oxidation with [Cp2 Fe]BF4 then affords a high yield of neutral 2 (Cp=η5 -cyclopentadienyl). Moreover, electrochemical studies indicate that a second one-electron reduction affords the diamagnetic dianion. Both anionic products were isolated and characterized by SC-XRD and their electronic structures were investigated by UV-vis spectro-electrochemistry, EPR and NMR spectroscopy, and DFT studies. These studies show that reduction proceeds primarily on the ligand, with (N2 S2 )4- containing both thiolate and ring-delocalized anions.

Synthesis, characterization, DNA binding interactions, DFT calculations, and Covid-19 molecular docking of novel bioactive copper(I) complexes developed via unexpected reduction of azo-hydrazo ligands

In this work, we focused on the 3rd goal of the sustainable development plan: achieving good health and supporting well-being. Two redox-active hydrazo ligands namely, phenylcarbonohydrazonoyldicyanide (PCHD) and pyridin-4-ylcarbonohydrazonoyl-dicyanide (PyCHD), and their copper(I) complexes have been synthesized and characterized. The analytical data indicates the formation of copper(I) complexes despite starting with copper(II) perchlorate salt. The 1H-NMR and UV–visible spectral studies in DMSO revealed that PyCHD mainly exists in its azo-form, while PCHD exists in azo ↔ hydrazo equilibrium form, and confirmed the copper(I) oxidation state. XPS, spectral and electrochemistry data indicated the existence of copper(I) valence of both complexes. Cyclic voltammetry of PCHD and its copper(I) complex supported the reduction power of the ligand. The antimicrobial activity, cytotoxicity against the mammalian breast carcinoma cell line (MCF7), and DNA interaction of the compounds are investigated. All compounds showed high antimicrobial, and cytotoxic activities, relative to the standard drugs. Upon studying the wheat DNA binding, PCHD and PyCHD were found to bind through external contacts, while both [Cu(PCHD)2]ClO4.H2O and [Cu(PyCHD)2]ClO4.H2O were intercalated binding. In-silico molecular docking simulations against Estrogen Receptor Alpha Ligand Binding Domain (ID: 6CBZ) were performed on all produced compounds and confirmed the invitro experimentally best anticancer activity of [Cu(PyCHD)2]ClO4.H2O. The molecular docking tests against SARS-CoV-2 main protease (ID: 6 WTT) showed promising activity in the order of total binding energy values: [Cu(PCHD)2]ClO4.H2O > [Cu(PyCHD)2]ClO4.H2O > PCHD > PyCHD.

Catalytic CO2 Reduction with Heptacoordinated Polypyridine Complexes: Switching the Selectivity via Metal Replacement.

The discovery of molecular catalysts for the CO2 reduction reaction (CO2 RR) in the presence of water, which are both effective and selective towards the generation of carbon-based products, is a critical task. Herein we report the catalytic activity towards the CO2 RR in acetonitrile/water mixtures by a cobalt complex and its iron analog both featuring the same redox-active ligand and an unusual seven-coordination environment. Bulk electrolysis experiments show that the cobalt complex mainly yields formate (52 % selectivity at an applied potential of -2.0 V vs Fc+ /Fc and 1 % H2 O) or H2 (up to 86 % selectivity at higher applied bias and water content), while the iron complex always delivers CO as the major product (selectivity >74 %). The different catalytic behavior is further confirmed under photochemical conditions with the [Ru(bpy)3 ]2+ sensitizer (bpy=2,2'-bipyridine) and N,N-diisopropylethylamine as electron donor, where the cobalt complex leads to preferential H2 formation (up to 89 % selectivity), while the iron analog quantitatively generates CO (up to 88 % selectivity). This is ascribed to a preference towards a metal-hydride vs. a metal-carboxyl pathway for the cobalt and the iron complex, respectively, and highlights how metal replacement may effectively impact on the reactivity of transition metal complexes towards solar fuel formation.

Exploring the Multifarious Role of the Ligand in Electrocatalytic Hydrogen Evolution Reaction Pathways.

In recent years, researchers have shifted their focus towards investigating the redox properties of ancillary ligand backbones for small-molecule activation. Several metal complexes have been reported for the electrocatalytic H2 evolution reaction (HER), providing valuable mechanistic insights. This process involves efficient coupling of electrons and protons. Redox-active ligands stipulate internal electron transfer and promote effective orbital overlap between metal and ligand, thereby, enabling efficient proton-coupled electron transfer reactions. Understanding such catalytic mechanisms requires thorough spectroscopic and computational analyses. Herein, we summarize recent examples of molecular electrocatalysts based on 3d transition metals that have significantly influenced mechanistic pathways, thus, emphasizing the multifaceted role of metal-ligand cooperativity.

Cobalt and nickel homobinuclear metallomacrocycles based on the redox-active bis-semiquinonato ligands as potential functional absorbing materials

Recently obtained bis-o-quinone with resorcinol as a bridge was utilized for synthesis of cobalt and nickel homobinuclear complexes. Two bis-o-semiquinonato metal fragments are situated co-facially to each other forming metallomacrocycle. Metals in both fragments bond diethyl ether solvate molecules externally as well as internally in the cell. At 100 K one of two metal atoms in the macrocycle is five-coordinated whereas the other one is six-coordinated due to internal solvent molecule. Heating to room temperature results in disordering of internal solvent molecule in two positions: coordinated to different nickel atoms. Variable temperature magnetic measurements indicate both complexes to be bis-o-semiquinonato anion-radical adducts of high spin metals with magnetic interactions inside of bis-o-semiquinonato units. Sign and energy of interactions depend on the coordination number of metal. Exchange interactions between units are weak. UV–Vis absorption spectrum is determined by ligands centered bands. CV indicates reversible reduction processes involving redox active dioxolene ligands.

Unexpected transformations of an allyl group in a gallium complex with the redox-active dpp-bian ligand

Unexpected transformations of an allyl group in a gallium complex with the redox-active dpp-bian ligand

Energy-efficient CO2/CO interconversion by homogeneous copper-based molecular catalysts

Facile conversion of CO2 to commercially viable carbon feedstocks offer a unique way to adopt a net-zero carbon scenario. Synthetic CO2-reducing catalysts have rarely exhibited energy-efficient and selective CO2 conversion. Here, the carbon monoxide dehydrogenase (CODH) enzyme blueprint is imitated by a molecular copper complex coordinated by redox-active ligands. This strategy has unveiled one of the rarest examples of synthetic molecular complex-driven reversible CO2reduction/CO oxidation catalysis under regulated conditions, a hallmark of natural enzymes. The inclusion of a proton-exchanging amine groups in the periphery of the copper complex provides the leeway to modulate the biases of catalysts toward CO2 reduction and CO oxidation in organic and aqueous media. The detailed spectroelectrochemical analysis confirms the synchronous participation of copper and redox-active ligands along with the peripheral amines during this energy-efficient CO2reduction/CO oxidation. This finding can be vital in abating the carbon footprint-free in multiple industrial processes.

Fate of Oxidation States at Actinide Centers in Redox-Active Ligand Systems Governed by Energy Levels of 5 f Orbitals.

We report the formation of a NpIV complex from the complexation of NpVI O2 2+ with the redox-active ligand tBu-pdiop2- =2,6-bis[N-(3,5-di-tert-butyl-2-hydroxyphenyl)iminomethyl]pyridine. To the best of our knowledge, this is the first example of the direct complexation-induced chemical reduction of NpVI O2 2+ to NpIV . In contrast, the complexation of UVI O2 2+ with tBu-pdiop2- did not induce the reduction of UVI O2 2+ , not even after the two-electron electrochemical reduction of [UVI O2 (tBu-pdiop)]. This contrast between the Np and U systems may be ascribed to the decrease of the energy of the 5 f orbitals in Np compared to those in U. The present findings indicate that the redox chemistry between UVI O2 2+ and NpVI O2 2+ should be clearly differentiated in redox-active ligand systems.

CO2 Activation with Manganese Tricarbonyl Complexes by an H-Atom Responsive Benzimidazole Ligand.

Herein, we report the synthesis and characterization of two manganese tricarbonyl complexes, MnI (HL)(CO)3 Br (1 a-Br) and MnI (MeL)(CO)3 Br (1 b-Br) (where HL=2-(2'-pyridyl)benzimidazole; MeL=1-methyl-2-(2'-pyridy)benzimidazole) and assayed their electrocatalytic properties for CO2 reduction. A redox-active pyridine benzimidazole ancillary ligand in complex 1 a-Br displayed unique hydrogen atom transfer ability to facilitate electrocatalytic CO2 conversion at a markedly lower reduction potential than that observed for 1 b-Br. Notably, a one-electron reduction of 1 a-Br yields a structurally characterized H-bonded binuclear Mn(I) adduct (2 a') rather than the typically observed Mn(0)-Mn(0) dimer, suggesting a novel method for CO2 activation. Combining advanced electrochemical, spectroscopic, and single crystal X-ray diffraction techniques, we demonstrate the use of an H-atom responsive ligand may reveal an alternative, low-energy pathway for CO2 activation by an earth-abundant metal complex catalyst.