Earth-abundant First-row Transition Metals Research Articles

Mononuclear Non-Heme Manganese-Catalyzed Enantioselective cis-Dihydroxylation of Alkenes Modeling Rieske Dioxygenases.

The practical catalytic enantioselective cis-dihydroxylation of olefins that utilize earth-abundant first-row transition metal catalysts under environmentally friendly conditions is an important yet challenging task. Inspired by the cis-dihydroxylation reactions catalyzed by Rieske dioxygenases and non-heme iron models, we report the biologically inspired cis-dihydroxylation catalysis that employs an inexpensive and readily available mononuclear non-heme manganese complex bearing a tetradentate nitrogen-donor ligand and aqueous hydrogen peroxide (H2O2) and potassium peroxymonosulfate (KHSO5) as terminal oxidants. A wide range of olefins are efficiently oxidized to enantioenriched cis-diols in practically useful yields with excellent cis-dihydroxylation selectivity and enantioselectivity (up to 99% ee). Mechanistic studies, such as isotopically 18O-labeled water experiments, and density functional theory (DFT) calculations support that a manganese(V)-oxo-hydroxo (HO-MnV═O) species, which is formed via the water-assisted heterolytic O-O bond cleavage of putative manganese(III)-hydroperoxide and manganese(III)-peroxysulfate precursors, is the active oxidant that effects the cis-dihydroxylation of olefins; this is reminiscent of the frequently postulated iron(V)-oxo-hydroxo (HO-FeV═O) species in the catalytic arene and alkene cis-dihydroxylation reactions by Rieske dioxygenases and synthetic non-heme iron models. Further, DFT calculations for the mechanism of the HO-MnV═O-mediated enantioselective cis-dihydroxylation of olefins reveal that the first oxo attack step controls the enantioselectivity, which exhibits a high preference for cis-dihydroxylation over epoxidation. In this study, we are able to replicate both the catalytic function and the key chemical principles of Rieske dioxygenases in mononuclear non-heme manganese-catalyzed enantioselective cis-dihydroxylation of olefins.

Exploiting the Marcus inverted region for first-row transition metal-based photoredox catalysis.

Second- and third-row transition metal complexes are widely employed in photocatalysis, whereas earth-abundant first-row transition metals have found only limited use because of the prohibitively fast decay of their excited states. We report an unforeseen reactivity mode for productive photocatalysis that uses cobalt polypyridyl complexes as photocatalysts by exploiting Marcus inverted region behavior that couples increases in excited-state energies with increased excited-state lifetimes. These cobalt (III) complexes can engage in bimolecular reactivity by virtue of their strong redox potentials and sufficiently long excited-state lifetimes, catalyzing oxidative C(sp2)-N coupling of aryl amides with challenging sterically hindered aryl boronic acids. More generally, the results imply that chromophores can be designed to increase excited-state lifetimes while simultaneously increasing excited-state energies, providing a pathway for the use of relatively abundant metals as photoredox catalysts.

Coupled Potential Energy Surfaces Strongly Impact the Lowest-Energy Spin-Flip Transition in Six-Coordinate Nickel(II) Complexes.

Luminescent complexes of earth-abundant first-row transition metals are of renewed, broad interest due to their spectroscopic and photochemical properties as well as emerging applications. New strong-field polypyridine ligands have led to six-coordinate 3d3 chromium(III) complexes with intense spin-flip luminescence in solution at room temperature. The ground and emissive states both arise from the (t2)3 electron configuration involving the dπ levels (O point group symmetry labels). Pseudoctahedral 3d8 nickel(II) complexes with such strong ligands are a priori also promising candidates for spin-flip luminescence. In contrast, the relevant electron configurations involve the dσ orbitals and (e)2 configurations. We have prepared the known nickel(II) complexes [Ni(terpy)2]2+, [Ni(phen)3]2+, and [Ni(ddpd)2]2+ as well as the novel complexes [Ni(dgpy)2]2+ and [Ni(tpe)2]2+ forming a series with increasing ligand field strengths (terpy = 2,2':6',2″-terpyridine; phen = 1,10-phenanthroline; ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine; dgpy = 2,6-diguanidylpyridine; tpe = 1,1,1-tris(pyrid-2-yl)ethane). The lowest-energy singlet and triplet excited states of these nickel(II) complexes are analyzed based on absorption spectra using ligand field theory and CASSCF-NEVPT2 calculations for vertical transition energies and a model based on coupled potential energy surfaces, leading to calculated absorption spectra in good agreement with the experimental data. No photoluminescence signal was observed in the wavelength ranges identified through the analyses of the absorption spectra. The models provide insight into key differences between the nickel(II) complexes and their strongly luminescent chromium(III) analogues.

Ni-Catalyzed Enantioselective Hydrofunctionalizations of 1,3-Dienes.

Ni-catalyzed enantioselective hydrofunctionalizations of conjugated dienes are particularly demanding reactions to devise because they require not only addressing the inherent challenges associated with the development of an enantioselective transformation but also overcoming all other aspects of selective catalysis (chemoselectivity, regioselectivity, diastereoselectivity, etc.). However, the value-added nature of the chiral allylic and homoallylic derivatives obtained by these methods, the lack of efficient alternatives, and the use of an earth-abundant first-row transition metal have led to renewed interest over the past decade. In this Perspective, we give an overview of the developments in this field, from the original findings (often dating back to the last century) to the most recent contributions. Emphasis is placed on the nature of the hydrofunctionalization agent (C(sp), C(sp2), C(sp3), N, P, or O).

Recent advances in earth-abundant first-row transition metal (Fe, Co and Ni)-based electrocatalysts for the oxygen evolution reaction

The oxygen evolution reaction (OER) is of fundamental importance as a half reaction and rate-controlling step that plays a predominant function in improving the energy storage and conversion efficiency during the electrochemical water-splitting process. In this review, after briefly introducing the fundamental mechanism of the OER, we systematically summarize the recent research progress for nonprecious-metal-based OER electrocatalysts of representative first-row transition metal (Fe, Co and Ni)-based composite materials. We analyze the effects of the physicochemical properties, including morphologies, structures and compositions, on the integrated performance of these OER electrocatalysts, with the aim of determining the structure-function correlation of the electrocatalysts in the electrochemical reaction process. Furthermore, the prospective development directions of OER electrocatalysts are also illustrated and emphasized. Finally, this mini-review highlights how systematic introductions will accelerate the exploitation of high-efficiency OER electrocatalysts.

Copper-Catalyzed Direct sp2 C-H Silylation of Arylamides Using Disilanes.

A copper-catalyzed method for direct intermolecular ortho-silylation of benzamides has been developed that affords organosilane products in moderate to high yields. The key features include: (i) use of commercially available disilanes as a silicon source with 8-aminoquinoline as a bidentate directing group, (ii) use of earth-abundant first-row transition metal, (iii) operationally simple conditions without the need of an inert atmosphere, and (iv) tolerance of a wide range of functional groups. The practicality and effectiveness of this method have been demonstrated by a gram-scale experiment. This strategy, therefore, constitutes a convenient way of constructing C-Si bonds useful for synthetic organic chemistry.

Design of molecular water oxidation catalysts with earth-abundant metal ions.

The four-electron oxidation of water (2H2O → O2 + 4H+ + 4e-) is considered the main bottleneck in artificial photosynthesis. In nature, this reaction is catalysed by a Mn4CaO5 cluster embedded in the oxygen-evolving complex of photosystem II. Ruthenium-based complexes have been successful artificial molecular catalysts for mimicking this reaction. However, for practical and large-scale applications in the future, molecular catalysts that contain earth-abundant first-row transition metal ions are preferred owing to their high natural abundance, low risk of depletion, and low costs. In this review, the frontier of water oxidation reactions mediated by first-row transition metal complexes is described. Special attention is paid towards the design of molecular structures of the catalysts and their reaction mechanisms, and these factors are expected to serve as guiding principles for creating efficient and robust molecular catalysts for water oxidation using ubiquitous elements.

Cp*Co(III)-Catalyzed C-H Hydroarylation of Alkynes and Alkenes and Beyond: A Versatile Synthetic Tool.

The use of earth-abundant first-row transition metals, such as cobalt, in C–H activation reactions for the construction and functionalization of a wide variety of structures has become a central topic in synthetic chemistry over the last few years. In this context, the emergence of cobalt catalysts bearing pentamethylcyclopentadienyl ligands (Cp*) has had a major impact on the development of synthetic methodologies. Cp*Co(III) complexes have been proven to possess unique reactivity compared, for example, to their Rh(III) counterparts, obtaining improved chemo- or regioselectivities, as well as yielding new reactivities. This perspective is focused on recent advances on the alkylation and alkenylation reactions of (hetero)arenes with alkenes and alkynes under Cp*Co(III) catalysis.

A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution.

Luminescence from Earth-abundant metal ions in solution at room temperature is a very challenging objective due to the intrinsically weak ligand field splitting of first-row transition metal ions, which leads to efficient nonradiative deactivation via metal-centered states. Only a handful of 3dn metal complexes (n ≠ 10) show sizable luminescence at room temperature. Luminescence in the near-infrared spectral region is even more difficult to achieve as further nonradiative pathways come into play. No Earth-abundant first-row transition metal complexes have displayed emission >1000 nm at room temperature in solution up to now. Here, we report the vanadium(III) complex mer-[V(ddpd)2][PF6]3 yielding phosphorescence around 1100 nm in valeronitrile glass at 77 K as well as at room temperature in acetonitrile with 1.8 × 10-4% quantum yield (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine). In addition, mer-[V(ddpd)2][PF6]3 shows very strong blue fluorescence with 2% quantum yield in acetonitrile at room temperature. Our comprehensive study demonstrates that vanadium(III) complexes with d2 electron configuration constitute a new class of blue and NIR-II luminophores, which complement the classical established complexes of expensive precious metals and rare-earth elements.

(Invited) Electronic Structures of Metal Centers in OER Catalyst Models and Electron/Energy Relays in the Excited State Supramolecular Dinuclear Transition Metal Complexes

Electronic Structures of Metal Centers in an OER Catalyst Model. One of the challenges in solar fuels generation is generating multiple redox equivalents for the oxygen evolution reaction (OER) (i.e., 2H2O→O2+4H++4e-) that is a four-electron, four-proton coupled process. Earth-abundant first-row transition metal oxides of cobalt, nickel, and their mixed-metal forms can drive this half-reaction at relatively low overpotentials. In collaboration with Nocera Group, we used a combination of in situ and ex situ X-ray absorption and emission spectroscopies as well as quantum mechanical calculations on OER thin films and their molecular and heterogeneous inorganic analogs. These studies provided insights into the electronic structures of the high-valent states involved in the mechanisms of O-O bond formation and for the high-valent states to drive the bond-forming and bond-breaking steps of OER reactions. Using a Co4O4 cluster as a model for the Co-based OER anode, CoPi, which has a similar topology and can host a stable, but electronically delocalized, mixed-valent Co(IV) state, we employed complementary X-ray spectroscopies, X-ray absorption (XAS) and 1s3p resonant inelastic X-ray scattering (Kβ RIXS), to effectively extract Co(IV) contributions within a spectroscopically active background (Figure 1). Co K- and L-edge X-ray absorption directly probe the 3d-manifold of effectively localized Co(IV), providing a handle on the covalency of the dπ-based redox active molecular orbital (MO) of Co4O4. Kβ RIXS is shown to be highly sensitive to metal cluster oxidation state and oxo-mediated metal-metal coupling in high-valent, delocalized mixed-valent species. We also probed the doubly oxidized Co(III)2(IV)2 state of the Co4O4 cluster, which features a cofacial Co(IV)2 site and is thus a molecular model of the active site in Co-OEC. Electron and Energy Relays in the Excited State Supramolecular Dinuclear Transition Metal Complexes. The rational design of multinuclear transition metal complexes (TMCs) for photochemical catalysis of homogeneous and/or heterogeneous multi-electron reactions (e.g. for producing solar fuels) requires a detailed understanding of the often unique and convoluted excited state charge and energy transfer dynamics in this class of compounds. Using combined optical and X-ray transient spectroscopic measurements, excited state electron electron relays in tetrapyridophenazine-bridged heteroleptic dinuclear Cu(I) bis(phenanthroline) complexes have been investigated as an exemplary system.

Secondary-Sphere Effects in Molecular Electrocatalytic CO2 Reduction.

The generation of fuels and value-added chemicals from carbon dioxide (CO2) using electrocatalysis is a promising approach to the eventual large-scale utilization of intermittent renewable energy sources. To mediate kinetically and thermodynamically challenging transformations of CO2, early reports of molecular catalysts focused primarily on precious metal centers. However, through careful ligand design, earth-abundant first-row transition metals have also demonstrated activity and selectivity for electrocatalytic CO2 reduction. A particularly effective and promising approach for enhancement of reaction rates and efficiencies of molecular electrocatalysts for CO2 reduction is the modulation of the secondary coordination sphere of the active site. In practice, this has been achieved through the mimicry of enzyme structures: incorporating pendent Brønsted acid/base sites, charged residues, sterically hindered environments, and bimetallic active sites have all proved to be valid strategies for iterative optimization. Herein, the development of secondary-sphere strategies to facilitate rapid and selective CO2 reduction is reviewed with an in-depth examination of the classic [Fe(tetraphenylporphyrin)]+, [Ni(cyclam)]2+, Mn(bpy)(CO)3X, and Re(bpy)(CO)3X (X = solvent or halide) systems, including relevant highlights from other recently developed ligand platforms.

Hydroarylations by cobalt-catalyzed C-H activation.

As an earth-abundant first-row transition metal, cobalt catalysts offer a broad range of economical methods for organic transformations via C–H activation. One of the transformations is the addition of C–H to C–X multiple bonds to afford alkylation, alkenation, amidation, and cyclization products using low- or high-valent cobalt catalysts. This hydroarylation is an efficient approach to build new C–C bonds in a 100% atom-economical manner. In this review, the recent developments of Co-catalyzed hydroarylation reactions and their mechanistic studies are summarized.

Mononuclear complexes of a tridentate redox-active ligand with sulfonamido groups: structure, properties, and reactivity.

The design of molecular complexes of earth-abundant first-row transition metals that can catalyze multi-electron C-H bond activation processes is of interest for achieving efficient, low-cost syntheses of target molecules. To overcome the propensity of these metals to perform single-electron processes, redox-active ligands have been utilized to provide additional electron equivalents. Herein, we report the synthesis of a novel redox active ligand, [ibaps]3-, which binds to transition metals such as FeII and CoII in a meridional fashion through the three anionic nitrogen atoms and provides additional coordination sites for other ligands. In this study, the neutral bidentate ligand 2,2'-bipyridine (bpy) was used to complete the coordination spheres of the metal ions and form NEt4[MII(ibaps)bpy] (M = Fe (1) or Co (1-Co)) salts. The FeII salt exhibited rich electrochemical properties and could be chemically oxidized by 1 and 2 equiv. of ferrocenium to form singly and doubly oxidized species, respectively. The reactivity of 1 towards intramolecular C-H bond amination of aryl azides at benzylic and aliphatic carbon centers was explored, and moderate to good yields of the resulting indoline products were obtained.

Mechanism of Ni-catalyzed selective C[sbnd]O cleavage of lignin model compound benzyl phenyl ether under mild conditions

Selective cleavage of CO bonds in benzyl phenyl ether (BPE) as a typical lignin α-O-4 ether to produce aromatics is a challenging and attractive topic. Herein, the earth-abundant first-row transition metals, such as Co, Ni and Cu were supported on activated carbon (Co/AC, Ni/AC and Cu/AC) to identify their ability for cleaving CO bond of BPE. Among these catalysts, Ni/AC exhibit highest activity for cleavage of CO bond. The reaction with BPE was carried out at pretty mild condition of 140 °C and 2 MPa H2, which is highly selective afforded toluene and phenol as the major products with the optimum yields of 88.5 and 86.5%, respectively. Based on the test, the reaction pathways were proposed. A abundant of dissociated H· atoms on Ni(0) sites forms surface active NiH species; Ni(0) activates and facilitates cleavage of the CO bond in BPE to form benzyl (C6H5C·) and phenoxy radicals (C6H5O·); H· atoms spill from active species NiH recombined together with C6H5C· and C6H5O· forming the products of toluene and phenol, respectively.

High-valent states in cobalt and nickel oxygen-evolving catalysts and their role in O—O bond formation

The solar-to-fuels conversion is a promising alternative to traditional energy sources such as fossil fuels, and the overall efficiency relies heavily on catalysts of the oxygen evolution half-reaction (i.e., 2H_2O → O_2 + 4H^+ + 4e^–). This four-electron, four-proton coupled reaction ultimately provides the reducing equivalents for solar fuels synthesis. Earth-abundant first-row transition metal oxides of cobalt, nickel, and their mixed-metal forms can drive this half-reaction at relatively low overpotentials. This presentation will discuss recent studies utilizing a combination of in situ and ex situ optical and X-ray spectroscopies, including resonant inelastic X-ray scattering, on oxygen-evolving thin films and their molecular and heterogeneous inorganic analogs. Experiment coupled with density functional theory calculations has provided insights into the electronic structures of the high-valent states involved in the mechanism of O–O bond formation.

Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

ChemInform Abstract: Exploration of Earth‐Abundant Transition Metals (Fe, Co, and Ni) as Catalysts in Unreactive Chemical Bond Activations

AbstractReview: 70 refs.

Exploration of earth-abundant transition metals (Fe, Co, and Ni) as catalysts in unreactive chemical bond activations.

Activation of inert chemical bonds, such as C-H, C-O, C-C, and so on, is a very important area, to which has been drawn much attention by chemists for a long time and which is viewed as one of the most ideal ways to produce valuable chemicals. Under modern chemical bond activation logic, many conventionally viewed "inert" chemical bonds that were intact under traditional conditions can be reconsidered as novel functionalities, which not only avoids the tedious synthetic procedures for prefunctionalizations and the emission of undesirable wastes but also inspires chemists to create novel synthetic strategies in completely different manners. Although activation of "inert" chemical bonds using stoichiometric amounts of transition metals has been reported in the past, much more attractive and challenging catalytic transformations began to blossom decades ago. Compared with the broad application of late and noble transition metals in this field, the earth-abundant first-row transition-metals, such as Fe, Co, and Ni, have become much more attractive, due to their obvious advantages, including high abundance on earth, low price, low or no toxicity, and unique catalytic characteristics. In this Account, we summarize our recent efforts toward Fe, Co, and Ni catalyzed "inert" chemical bond activation. Our research first unveiled the unique catalytic ability of iron catalysts in C-O bond activation of both carboxylates and benzyl alcohols in the presence of Grignard reagents. The benzylic C-H functionalization was also developed via Fe catalysis with different nucleophiles, including both electron-rich arenes and 1-aryl-vinyl acetates. Cobalt catalysts also showed their uniqueness in both aromatic C-H activation and C-O activation in the presence of Grignard reagents. We reported the first cobalt-catalyzed sp(2) C-H activation/arylation and alkylation of benzo[h]quinoline and phenylpyridine, in which a new catalytic pathway via an oxidative addition process was demonstrated to be much preferable. Another interesting discovery was the Co-catalyzed magnesiation of benzylic alcohols in the presence of different Grignard reagents, which proceeded via Co-mediated selective C-O bond activation. In C-O activation, Ni catalysts were found to be most powerful, showing the high efficacy in different kinds of couplings starting form "inert" O-based electrophiles. In addition, Ni catalysts exhibited their power in C-H and C-C activation, which have been proven by us and pioneers in this field. Notably, our developments indicated that the catalytic efficacy in cross coupling between aryl bromides and arenes under mild conditions was not the privilege of several noble metals; most of the transition metals exhibited credible catalytic ability, including Fe, Co, and Ni. We hope our studies inspire more interest in the development of first row transition metal-catalyzed inert chemical bond functionalization.

ChemInform Abstract: Low‐Valent Cobalt Catalysis: New Opportunities for C—H Functionalization

AbstractReview: 76 refs.

Low-Valent Cobalt Catalysis: New Opportunities for C–H Functionalization

Rapid progress in the fields of organometallic chemistry and homogeneous catalysis has made it possible for synthetic chemists to consider using ubiquitous yet unreactive C-H bonds as starting points to construct complex organic molecules. However, a majority of the C-H functionalization reactions currently in use require noble transition metal catalysts and harsh reaction conditions, so researchers have placed a priority on the development of mild and cost-effective catalysts. Given this situation, we wondered whether earth-abundant first-row transition metals could emulate the reactivity of a noble transition metal catalyst and carry out similar C-H functionalization reactions at a lower cost and under milder conditions. We also wondered whether we could use first-row transition metals to achieve hitherto unknown, but useful, C-H functionalization reactions. This Account summarizes our research on the development of three different types of C-H functionalization reactions using low-valent cobalt catalysts: (1) hydroarylation of alkynes and olefins, (2) ortho C-H functionalization with electrophiles, and (3) addition of arylzinc reagents to alkynes involving 1,4-cobalt migration. Although synthetic chemists have previously paid little attention to cobalt in designing catalytic C-H functionalization reactions, earlier studies, particularly those on stoichiometric cyclometalation, inspired us as we developed the hydroarylation and ortho C-H functionalization reactions. In these transformations, we combined a cobalt precatalyst, a ligand (such as phosphine or N-heterocyclic carbene (NHC)), and Grignard reagent to generate low-valent cobalt catalysts. These novel catalysts promoted a series of pyridine- and imine-directed hydroarylation reactions of alkynes and olefins at mild temperatures. Notably, we observed branched-selective addition to styrenes, which highlights a distinct regioselectivity of the cobalt catalyst compared with typical rhodium and ruthenium catalysts. The combination of a cobalt-NHC catalyst and a Grignard reagent allows directed aromatic C-H functionalizations with electrophiles such as aldimines, aryl chlorides, and alkyl chlorides or bromides. This second reaction has a particularly broad scope, allowing us to introduce secondary alkyl groups at the ortho position of aryl imines, a difficult reaction to carry out by other means. Serendipitously, we found that a cobalt-Xantphos complex catalyzed the third type of C-H functionalization: the addition of an arylzinc reagent to an alkyne to afford ortho-alkenylarylzinc species through a 1,4-cobalt migration. This "migratory arylzincation" allowed us to quickly construct a diverse group of functionalized benzothiophenes and benzoselenophenes. Collectively, our studies of cobalt catalysis have provided cost-effective catalysts and milder conditions for existing C-H functionalizations and have led to some unprecedented, attractive chemical transformations.