Reduction of CO to Methanol with Recyclable Organic Hydrides.

The reaction steps for the selective conversion of a transition metal carbonyl complex to a hydroxymethyl complex that releases methanol upon irradiation with visible light have been successfully quantified in acetonitrile solution with dihydrobenzimidazole organic hydride reductants. Dihydrobenzimidazole reductants have been shown to be inactive toward H2 generation in the presence of a wide range of proton sources and have been regenerated electrochemically or photochemically. Specifically, the reaction of cis-[Ru(bpy)2(CO)2]2+ (bpy = 2,2'-bipyridine) with one equivalent of a dihydrobenzimidazole quantitatively yields a formyl complex, cis-[Ru(bpy)2(CO)(CHO)]+, and the corresponding benzimidazolium on a seconds time scale. Kinetic experiments revealed a first-order dependence on the benzimidazole hydride concentration and an unusually large kinetic isotope effect, inconsistent with direct hydride transfer and more likely to occur by an electron transfer-proton-coupled electron transfer (EΤ-PCET) or related mechanism. Further reduction/protonation of cis-[Ru(bpy)2(CO)(CHO)]+ with two equivalents of the organic hydride yields the hydroxymethyl complex cis-[Ru(bpy)2(CO)(CH2OH)]+. Visible light excitation of cis-[Ru(bpy)2(CO)(CH2OH)]+ in the presence of excess organic hydride was shown to yield free methanol. Identification and quantification of methanol as the sole CO reduction product was confirmed by 1H NMR spectroscopy and gas chromatography. The high selectivity and mild reaction conditions suggest a viable approach for methanol production from CO, and from CO2 through cascade catalysis, with renewable organic hydrides that bear similarities to Nature's NADPH/NADP+.

Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations.

Formal reduction potentials of highly oxidizing and short-lived radical cations of substituted biphenyls generated by pulse radiolysis in 1,2-dichloroethane (DCE) were measured using a redox equilibrium ladder method. The effect of halide ion-radical interactions on reduction potentials of biphenyls was examined by utilizing the ability of DCE to release Cl- in the vicinity of the radical cation. The Hammett correlation of measured potentials across a range of over 700 mV shows saturation at high Hammett sigma values. This effect has been explained by both ion-pairing and hemicolligation interactions between biphenyl radical cations and Cl- and appears to modulate reduction potentials by as much as 400 mV. This finding offers a convenient way to manipulate the energetics of electron transfer involving organic redox species.

Predicting Mössbauer Parameters of Nonheme Diiron Complexes with Density Functional Theory.

Mössbauer spectroscopy provides significant insights into the electronic structure and environment of the metal centers. Herein, we investigate the electronic structures of a set of nonheme diiron complexes by evaluating two key parameters pertaining to Mössbauer spectroscopy, namely, the isomer shift (δ) and quadrupole splitting (|ΔEQ|), using different levels of density functional theory (DFT). The diiron systems investigated here span diverse oxidation states, bridging motifs, and spin coupling patterns, which present a challenging case for theoretical predictions. We demonstrate that the combination of B97-D3/def2-TZVP is an efficient approach in modeling both the δ and |ΔEQ| values with high accuracy for the representative nonheme diiron complexes. We also show that δ is accurately predicted irrespective of the choice of approximate density functional while the |ΔEQ| is sensitive to the level of theory employed. Further investigation shows that the present methodology assessed using synthetic nonheme diiron complexes could be extended to nonheme diiron enzyme active sites, featuring both ferromagnetic and antiferromagnetic coupling between the iron centers.

A Dicationic fac-Re(bpy)(CO)3Cl for CO2 Electroreduction at a Reduced Overpotential.

A dicationic Re bipyridine-type complex, fac-Re(6,6'-(2-((trimethylammonio)-methyl)phenyl)-2,2'-bipyridine )(CO)3Cl hexafluorophosphate (12+), has been synthesized, and its electrochemical behavior under Ar and CO2 has been investigated. The presence of pendent tetra-alkylammonium cations induces an anodic shift in the electrocatalytic potential for CO2 reduction relative to structurally similar model complexes. The electrochemical mechanisms in anhydrous CH3CN and in the presence of weak acids (water or trifluoroethanol) have been analyzed using cyclic voltammetry assisted by infrared spectroelectrochemistry and theoretical calculations. The dication enables catalysis at a diminished potential through Coulombic stabilization of the doubly reduced pentacoordinate species, its CO2 adduct, the hydroxide anion, and the conjugate base formed during acid-assisted C-OH bond cleavage of the metallocarboxylic acid to the metallocarbonyl and H2O. The major reduction product is CO, but in the presence of trifluoroethanol, formate is also produced with 14% Faradaic efficiency.

Heterogeneous Electrochemical Ammonia Oxidation with a Ru-bda Oligomer Anchored on Graphitic Electrodes via CH-π Interactions.

Molecular catalysts can promote ammonia oxidation, providing mechanistic insights into the electrochemical N2 cycle for a carbon-free fuel economy. We report the ammonia oxidation activity of carbon anodes functionalized with the oligomer {[RuII(bda-κ-N 2 O 2)(4,4'-bpy)]10(4,4'-bpy)}, Rubda-10, where bda is [2,2'-bipyridine]-6,6'-dicarboxylate and 4,4'-bpy is 4,4'-bipyridine. Electrocatalytic studies in propylene carbonate demonstrate that the Ru-based hybrid anode used in a 3-electrode configuration transforms NH3 to N2 and H2 in a 1:3 ratio with near-unity faradaic efficiency at an applied potential of 0.1 V vs Fc+/0, reaching turnover numbers of 7500. X-ray absorption spectroscopic analysis after bulk electrolysis confirms the molecular integrity of the catalyst. Based on computational studies together with electrochemical evidence, ammonia nucleophilic attack is proposed as the primary pathway that leads to critical N-N bond formation.

Peroxide-Selective Reduction of O2 at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide.

Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La-Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93-99% O22-) reduction of dioxygen (O2) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([PrIII2(O22-)(18C6)2(EG)2][OTf]4; 18C6 = 18-crown-6, EG = ethylene glycol, -OTf = -O3SCF3; 2-Pr) was isolated and characterized by single-crystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. 2-Pr displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [pKa1(MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal-ligand binding events preceding electron transfer.

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides.

The kinetics of hydride transfer from Re(Rbpy)(CO)3H (bpy = 4,4'-R-2,2'-bipyridine; R = OMe, tBu, Me, H, Br, COOMe, CF3) to CO2 and seven different cationic N-heterocycles were determined. Additionally, the thermodynamic hydricities of complexes of the type Re(Rbpy)(CO)3H were established primarily using computational methods. Linear free-energy relationships (LFERs) derived by correlating thermodynamic and kinetic hydricities indicate that, in general, the rate of hydride transfer increases as the thermodynamic driving force for the reaction increases. Kinetic isotope effects range from inverse for hydride transfer reactions with a small driving force to normal for reactions with a large driving force. Hammett analysis indicates that hydride transfer reactions with greater thermodynamic driving force are less sensitive to changes in the electronic properties of the metal hydride, presumably because there is less buildup of charge in the increasingly early transition state. Bronsted α values were obtained for a range of hydride transfer reactions and along with DFT calculations suggest the reactions are concerted, which enables the use of Marcus theory to analyze hydride transfer reactions involving transition metal hydrides. It is notable, however, that even slight perturbations in the steric properties of the Re hydride or the hydride acceptor result in large deviations in the predicted rate of hydride transfer based on thermodynamic driving forces. This indicates that thermodynamic considerations alone cannot be used to predict the rate of hydride transfer, which has implications for catalyst design.

Steric and Lewis Basicity Influence of the Second Coordination Sphere on Electrocatalytic CO2 Reduction by Manganese Bipyridyl Complexes.

This study aims to provide a greater insight into the balance between steric (bpy vs (Ph)2bpy vs mes2bpy ligands) and Lewis basic ((Ph)2bpy vs (MeOPh)2bpy vs (MeSPh)2bpy ligands) influence on the efficiencies of the protonation-first vs reduction-first CO2 reduction mechanisms with [MnI(R2bpy)(CO)3(CH3CN)]+ precatalysts, and on their respective transition-state geometries/energies for rate-determining C-OH bond cleavage toward CO evolution. The presence of only modest steric bulk at the 6,6'-diphenyl-2,2'-bipyridyl ((Ph)2bpy) ligand has here allowed unique insight into the mechanism of catalyst activation and CO2 binding by navigating a perfect medium between the nonsterically encumbered bpy-based and the highly sterically encumbered mes2bpy-based precatalysts. Cyclic voltammetry conducted in CO2-saturated electrolyte for the (Ph)2bpy-based precatalyst [2-CH3CN]+ confirms that CO2 binding occurs at the two-electron-reduced activated catalyst [2]- in the absence of an excess proton source, in contrast to prior assumptions that all manganese catalysts require a strong acid for CO2 binding. This observation is supported by computed free energies of the parent-child reaction for [Mn-Mn]0 dimer formation, where increased steric hindrance relative to the bpy-based precatalyst correlates with favorable CO2 binding. A critical balance must be adhered to, however, as the absence of steric bulk in the bpy-based precatalyst [1-CH3CN]+ maintains a lower overpotential than [2-CH3CN]+ at the protonation-first pathway with comparable kinetic performance, whereas an ∼2-fold greater TOFmax is observed at its reduction-first pathway with an almost identical overpotential as [2-CH3CN]+. Notably, excessive steric bulk in the mes2bpy-based precatalyst [3-CH3CN]+ results in increased activation free energies of the C-OH bond cleavage transition states for both the protonation-first and the reduction-first pathways relative to both [1-CH3CN]+ and [2-CH3CN]+. In fact, [3-CH3CN]+ requires a 1 V window beyond its onset potential to reach its peak catalytic current, which is in contrast to the narrower (<0.30 V) potential response window of the remaining catalysts here studied. Voltammetry recorded under 1 atm of CO2 with 2.8 M (5%) H2O establishes [2-CH3CN]+ to have the lowest overpotential (η = 0.75 V) in the series here studied, attributed to its ability to lie "on the fence" when providing sufficient steric bulk to hinder (but not prevent) [Mn-Mn]0 dimerization, while simultaneously having a limited steric impact on the free energy of activation for the rate-determining C-OH bond cleavage transition state. While the methoxyphenyl bpy-based precatalyst [4-CH3CN]+ possesses an increased steric presence relative to [2-CH3CN]+, this is offset by its capacity to stabilize the C-OH bond cleavage transition states of both the protonation-first and the reduction-first pathways by facilitating second coordination sphere H-bonding stabilization.

Reorganization Energy of Electron Transfer in Ionic Liquids.

Bandshape analysis of charge-transfer optical bands in room-temperature ionic liquids (ILs) was performed to extract the reorganization energy of electron transfer. Remarkably, the reorganization energies in ILs are close to those in cyclohexane. This result runs against common wisdom in the field since conducting ILs, which are characterized by an infinite static dielectric constant, and nonpolar cyclohexane fall to the opposite ends of the polarity scale based on their dielectric constants. Theoretical calculations employing structure factors of ILs from molecular dynamics simulations support the low values of the reorganization energy. Standard dielectric arguments do not apply to solvation in ILs, and nonergodic reorganization energies are required for a quantitative analysis.

Mechanistic investigation of the aerobic oxidation of 2-pyridylacetate coordinated to a Ru(II) polypyridyl complex.

A new ruthenium polypyridyl complex, [Ru(bpy)2(acpy)]+ (acpy = 2-pyridylacetate, bpy = 2,2'-bipyridine), was synthesized and fully characterized. Distinct from the previously reported analog, [Ru(bpy)2(pic)]+ (pic = 2-pyridylcarboxylate), the new complex is unstable under aerobic conditions and undergoes oxidation to yield the corresponding α-keto-2-pyridyl-acetate (acpyoxi) coordinated to the RuII center. The reaction is one of the few examples of C-H activation at mild conditions using O2 as the primary oxidant and can provide mechanistic insights with important implications for catalysis. Theoretical and experimental investigations of this aerobic oxidative transformation indicate that it takes place in two steps, first producing the α-hydroxo-2-pyridyl-acetate analog and then the final product. The observed rate constant for the first oxidation was in the order of 10-2 h-1. The reaction is hindered in the presence of coordinating solvents indicating the role of the metal center in the process. Theoretical calculations at the M06-L level of theory were performed for multiple reaction pathways in order to gain insights into the most probable mechanism. Our results indicate that O2 binding to [Ru(bpy)2(acpy)]+ is favored by the relative instability of the six-ring chelate formed by the acpy ligand and the resulting RuIII-OO˙- superoxo is stabilized by the carboxylate group in the coordination sphere. C-H activation by this species involves high activation free energies (ΔG‡ = 41.1 kcal mol-1), thus the formation of a diruthenium µ-peroxo intermediate, [(RuIII(bpy)2(O-acpy))2O2]2+via interaction of a second [Ru(bpy)2(acpy)]+ was examined as an alternative pathway. The dimer yields two RuIVO centers with a low ΔG‡ of 2.3 kcal mol-1. The resulting RuIVO species can activate C-H bonds in acpy (ΔG‡ = 23.1 kcal mol-1) to produce the coordinated α-hydroxo-2-pyridylacetate. Further oxidation of this intermediate leads to the α-keto-2-pyridyl-acetate product. The findings provide new insights into the mechanism of C-H activation catalyzed by transition-metal complexes using O2 as the sole oxygen source.

An amide-based second coordination sphere promotes the dimer pathway of Mn-catalyzed CO2-to-CO reduction at low overpotential.

The [fac-Mn(bpy)(CO)3Br] complex is capable of catalyzing the electrochemical reduction of CO2 to CO with high selectivity, moderate activity and large overpotential. Several attempts have been made to lower the overpotential and to enhance the catalytic activity of this complex by manipulating the second-coordination sphere of manganese and using relatively stronger acids to promote the protonation-first pathway. We report herein that the complex [fac-Mn(bpy-CONHMe)(CO)3(MeCN)]+ ([1-MeCN]+; bpy-CONHMe = N-methyl-(2,2'-bipyridine)-6-carboxamide) as a pre-catalyst could catalyze the electrochemical reduction of CO2 to CO with low overpotential and high activity and selectivity. Combined experimental and computational studies reveal that the amide NH group not only decreases the overpotential of the Mn catalyst by promoting the dimer and protonation-first pathways in the presence of H2O but also enhances the CO2 electroreduction activity by facilitating C-OH bond cleavage, making [1-MeCN]+ an efficient CO2 reduction pre-catalyst at low overpotential.

Calcium-Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores.

Coupled dinuclear copper oxygen cores (Cu2 O2 ) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O2 transport and substrate oxidation in many organisms. µ-1,2-cis peroxido dicopper cores (C P) have been proposed as key structures in the early stages of O2 binding in these proteins; their reversible isomerization to other Cu2 O2 cores are directly relevant to enzyme function. Despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallic C P cores in biological and synthetic systems, the properties and reactivity of C P Cu2 O2 species remain largely unexplored. Herein, we report the reversible interconversion of µ-1,2-trans peroxido (T P) and C P dicopper cores. CaII mediates this process by reversible binding at the Cu2 O2 core, highlighting the unique capability for metal-ion binding events to stabilize novel reactive fragments and control O2 activation in biomimetic systems.

Synthesis, Characterization, and Water Oxidation Activity of Isomeric Ru Complexes.

The synthesis and characterization of the isomeric ruthenium complexes with the general formula cis- and trans-[Ru(trpy)(qc)X]n+ (trpy is 2,2':6',2″-terpyridine, qc is 8-quinolinecarboxylate, cis-1 and trans-1, X = Cl, n = 0; cis-2 and trans-2, X=OH2, n = 1) with respect to the relative disposition of the carboxylate and X ligands are reported. For comparison purposes, another set of ruthenium complexes with general formula cis- and trans-[Ru(trpy)(pic)(OH2)]+ (pic is 2-picolinate (cis-3, trans-3)) have been prepared. The complexes with a qc ligand show a more distorted geometry compared to the complexes with a pic ligand. In all of the cases, the trans isomers show lower potential values for all of the redox couples relative to the cis isomers. Complexes cis-2 and trans-2 with six-member chelate rings show higher catalytic activity than cis-3 and trans-3. Overall, it was shown that the electronic perturbation to the metal center exerted by different orientation and geometry of the ligands significantly influences both redox properties and catalytic performance.

Methane Generation from CO2 with a Molecular Rhenium Catalyst.

The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C1-Cn products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium tricarbonyl complexes coordinated by the asymmetric diimine ligands 2-(isoquinolin-1-yl)-4,5-dihydrooxazole (quin-1-oxa), 2-(quinolin-2-yl)-4,5-dihydrooxazole (quin-2-oxa), and 2-(isoquinolin-3-yl)-4,5-dihydrooxazole (quin-3-oxa) that catalyze the reduction of CO2 to carbon monoxide and methane, albeit the latter with a low efficiency. To our knowledge, these complexes are the first examples of rhenium(I) catalysts capable of converting carbon dioxide into methane. Re(quin-1-oxa)(CO)3Cl (1), Re(quin-2-oxa)(CO)3Cl (2), and Re(quin-3-oxa)(CO)3Cl (3) were characterized and studied using a variety of electrochemical and spectroscopic techniques. In bulk electrolysis experiments, the three complexes reduce CO2 to CO and CH4. When the controlled-potential electrolysis experiments are performed at -2.5 V (vs Fc+/0) and in the presence of the Brønsted acid 2,2,2-trifluoroethanol, methane is produced with turnover numbers that range from 1.3 to 1.8. Isotope labeling experiments using 13CO2 atmosphere produce 13CH4 (m/z = 17) confirming that methane originates from CO2 reduction. Theoretical calculations are performed to investigate the mechanistic aspects of the 8e-/8H+ reduction of CO2 to CH4. A ligand-assisted pathway is proposed to be an efficient pathway in the formation of CH4. Delocalization of the electron density on the (iso)quinoline moiety upon reduction stabilizes the key carbonyl intermediate leading to additional reactivity of this ligand. These results should aid the development of more robust catalytic systems that produce CH4 from CO2.

Efficient Iridium Catalysts for Formic Acid Dehydrogenation: Investigating the Electronic Effect on the Elementary ß-Hydride Elimination and Hydrogen Formation Steps.

We report herein a series of Cp*Ir complexes containing a rigid 8-aminoquinolinesulfonamide moiety as highly efficient catalysts for the dehydrogenation of formic acid (FA). The complex [Cp*Ir(L)Cl] (HL = N-(quinolin-8-yl)benzenesulfonamide) displayed a high turnover frequency (TOF) of 2.97 × 104 h-1 and a good stability (>100 h) at 60 °C. Comparative studies of [Cp*Ir(L)Cl] with the rigid ligand and [Cp*Ir(L')Cl] (HL' = N-propylpypridine-2-sulfonamide) without the rigid aminoquinoline moiety demonstrated that the 8-aminoquinoline moiety could dramatically enhance the stability of the catalyst. The electron-donating ability of the N,N'-chelating ligand was tuned by functionalizing the phenyl group of the L ligand with OMe, Cl, and CF3 to have a systematical perturbation of the electronic structure of [Cp*Ir(L)Cl]. Experimental kinetic studies and density functional theory (DFT) calculations on this series of Cp*Ir complexes revealed that (i) the electron-donating groups enhance the hydrogen formation step while slowing down the ß-hydride elimination and (ii) the electron-withdrawing groups display the opposite effect on these reaction steps, which in turn leads to lower optimum pH for catalytic activity compared to the electron-donating groups.

Oxygen Atom Transfer as an Alternative Pathway for Oxygen-Oxygen Bond Formation.

Fundamental understanding of catalytic mechanisms of water oxidation is a prerequisite for the design and development of efficient and rugged water oxidation catalysts. In this work, a detailed mechanistic study of the water oxidation mechanism of the [RuII(npm)(4-pic)2(H2O)]2+ (npm = 4-t-butyl-2,6-di(1',8'-naphthyrid-2'-yl)-pyridine, pic = 4-picoline) complex, [RuII-OH2]2+, reveals oxygen atom transfer from highly reactive ruthenium oxo intermediates to noncoordinating nitrogen atoms of the ligand as a novel route for oxygen evolution via storage of oxidizing equivalents as N-oxide groups on the ligand framework. Theoretical calculations show that the initial complex, [RuII-OH2]2+, is transformed to a di-N-oxide [RuII-OH2,(-NO)2]2+ complex upon oxidation via facile OAT steps from RuV=O species and that [RuV=O,(-NO)2]3+ represents the most likely reactive species for the critical O-O bond formation. Furthermore, a new stepwise mechanism for oxygen evolution is introduced, which proceeds via coupling of Ru-O and N-O moieties producing a peroxide intermediate, [RuV-OO-N,(-NO)]3+, and can compete with the water nucleophilic attack pathway for the oxygen evolution reaction. In this mechanism, a water molecule is oxidatively activated to an "oxygen atom" which is "stored" at a noncoordinating pyridine. Oxidative activation of a second water molecule, facilitated by coordination expansion of the intermediate N-oxide, generates the second oxygen atom required to produce a dioxygen molecule.

Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis.

A new Ru complex containing the deprotonated 2,2':6',2''-terpyridine-6,6''-diphosphonic acid (H4tPa) and pyridine (py) of general formula [RuII(H3tPa-κ-N3O)(py)2]+, 2+, has been prepared and thoroughly characterized by means of spectroscopic and electrochemical techniques, X-ray diffraction analysis, and density functional theory (DFT) calculations. Complex 2+ presents a dynamic behavior in the solution that involves the synchronous coordination and the decoordination of the dangling phosphonic groups of the tPa4- ligand. However, at oxidation state IV, complex 2+ becomes seven coordinated with the two phosphonic groups now bonded to the metal center. Further, at this oxidation state at neutral and basic pH, the Ru complex undergoes the coordination of an exogenous OH- group from the solvent that leads to an intramolecular aromatic O atom insertion into the CH bond of one of the pyridyl groups, forming the corresponding phenoxo-phosphonate Ru complex [RuIII(tPaO-κ-N2OPOC)(py)2]2-, 42-, where tPaO5- is the 3-(hydroxo-[2,2':6',2''-terpyridine]-6,6''-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 42-, has been isolated and spectroscopically and electrochemically characterized. In addition, a crystal structure has been also obtained using single-crystal X-ray diffraction techniques. Complex 42- turns out to be an exceptional water oxidation catalyst achieving record maximum turnover frequencies (TOFmax) on the order of 16 000 s-1. A mechanistic analysis complemented with DFT calculations has also been carried out, showing the critical role of intramolecular second coordination sphere effects exerted by the phosphonate groups in lowering the activation energy at the rate-determining step.

An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex.

The subject of this study [fac-Mn(bqn)(CO)3(CH3CN)]+ (bqn = 2,2'-biquinoline), is of particular interest because the bqn ligand exhibits both steric and electronic influence over the fundamental redox properties of the complex and, consequently, its related catalytic properties with respect to the activation of CO2. While not a particularly efficient catalyst for CO2 to CO conversion, in-situ generation and activity measurements of the [fac-Mn(bqn)(CO)3]- active catalyst allows for a better understanding of ligand design at the Mn center. By making direct comparisons to the related 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen), and 2,9-dimethyl-1,10-phenanthroline (dmphen) ligands via a combination of voltammetry, infrared spectroelectrochemistry, controlled potential electrolysis and computational analysis, the role of steric vs. electronic influences on the nucleophilicity of Mn-based CO2 reduction electrocatalysts is discussed.

Reactivity of bio-inspired Cu(II) (N2/Py2) complexes with peroxide at room temperature.

Developing coordination complexes of earth abundant metals that can perform substrate oxidations under benign conditions is an ongoing challenge. Herein, the reactivity of two mononuclear Cu-complexes toward the oxidant H2O2 is reported. Both complexes displayed ligand oxidation upon reaction with the oxidant. Analysis of spectroscopic data established that the respective product complexes contained mononuclear Cu(II) centers. Moreover, treatment of these Cu-complexes with oxidant in the presence of substrate resulted in the interception of ligand oxidation with preferential oxidation of the substrate. Computational studies identified plausible mechanistic pathways, suggesting a copper-oxyl intermediate as the likely reactive intermediate responsible for substrate and ligand oxidation. To our knowledge, this is the first Cu-mediated system that showed ligand oxidation, oxo-transfer capability, and external hydrocarbon oxidation under stoichiometric conditions.