3d Transition Metal Complexes Research Articles

A few examples of cis trans isomerization in complexes involving the oxamide function

Synthesis of heterodinuclear 3d transition metal complexes in which two metal ions are introduced in equivalent coordination sites of a ligand is quite uncommon. We have previously shown that the application of the cis–trans isomerization of the oxamido group was able to furnish such a possibility. In the present paper we demonstrate that this synthetic pathway, relying on the possibility of changing the conformation (cis vs trans) of the oxamido group, can be extended to other ligands. Although we have not been able to characterize these complexes by structural determinations, FAB-MS, EPR and magnetic data do confirm the efficiency of this reaction pathway. We also demonstrate that the cis–trans isomerization of the oxamido group is not due to a particular property of the ion involved in the reaction. In fact, isomerization is governed by the basicity of the reaction medium. According to the reaction condition, it is possible to favor or not this phenomenon, and to increase the accessibility to a larger number of novel genuine complexes. But the oxophilic character of the lanthanide ions limits the use of this synthetic pathway because it impedes this isomerization. Eventually, the very weak magnetic interactions observed in these Cu-Gd complexes can be explained thanks to spin polarization.

Enhanced Near-infrared Phosphorescent Emission Modulated by Clipping of Metallotweezers in Aqueous Media.

Near-infrared phosphorescent materials have received significant attention due to their potential applications in bioimaging and diagnostics. Although, many types of organic phosphors with near-infrared emission have been developed, the low phosphorescence efficiency in aqueous solution hampers their practical applications in biological systems. Hence, there is an urgent need to develop near-infrared phosphorescent materials with high emission efficiency in aqueous media. Metallotweezers, based on d8 transition metal complexes, emerge as the potential candidates for realizing this objective. Specifically, metallotweezers, featuring two positively charged platinum(II) terpyridine and neutral gold(III) diphenylpyridine pincers on diphenylpyridine spacer, have been designed and synthesized, respectively. The pre-organization effect, rendered by the rigid spacer, enables the resulting metallotweezers to complex with each other, resulting in the formation of clipping complex. The synergistic rigidifying and shielding effects of clipping structure results in enhanced phosphorescent emission intensity. Concurrently, due to phase segregation between the clipping units and the polyethylene glycol tail, the clipping complex undergoes self-assembly in aqueous solution, resulting in phosphorescent emission in the near-infrared region. Overall, non-covalent clipping of metallotweezers illustrated in this study presents a new and effective approach toward near-infrared phosphorescent materials.

Exploring the Role and Variability of 3d Transition Metal Complexes in Artistic Coloration through a Bottom-Up Scientific Approach

Exploring the Role and Variability of 3d Transition Metal Complexes in Artistic Coloration through a Bottom-Up Scientific Approach

LigandDiff: de Novo Ligand Design for 3D Transition Metal Complexes with Diffusion Models.

Transition metal complexes are a class of compounds with varied and versatile properties, making them of great technological importance. Their applications cover a wide range of fields, either as metallodrugs in medicine or as materials, catalysts, batteries, solar cells, etc. The demand for the novel design of transition metal complexes with new properties remains of great interest. However, the traditional high-throughput screening approach is inherently expensive and laborious since it depends on human expertise. Here, we present LigandDiff, a generative model for the de novo design of novel transition metal complexes. Unlike the existing methods that simply extract and combine ligands with the metal to get new complexes, LigandDiff aims at designing configurationally novel ligands from scratch, which opens new pathways for the discovery of organometallic complexes. Moreover, it overcomes the limitations of current methods, where the diversity of new complexes highly relies on the diversity of available ligands, while LigandDiff can design numerous novel ligands without human intervention. Our results indicate that LigandDiff designs unique and novel ligands under different contexts, and these generated ligands are synthetically accessible. Moreover, LigandDiff shows good transferability by generating successful ligands for any transition metal complex.

Recent Advances in the Structure Elucidation of d10 transition metal Complexes based on 16-membered ring macrolide Drug

Recent Advances in the Structure Elucidation of d10 transition metal Complexes based on 16-membered ring macrolide Drug

Stimulated X-ray emission spectroscopy.

We describe an emerging hard X-ray spectroscopy technique, stimulated X-ray emission spectroscopy (S-XES). S-XES has the potential to characterize the electronic structure of 3d transition metal complexes with spectral information currently not reachable and might lead to the development of new ultrafast X-ray sources with properties beyond the stateoftheart. S-XES has become possible with the emergence of X-ray free-electron lasers (XFELs) that provide intense femtosecond X-ray pulses that can be employed to generate a population inversion of core-hole excited states resulting in stimulated X-ray emission. We describe the instrumentation, the various types of S-XES, the potential applications, the experimental challenges, and the feasibility of applying S-XES to characterize dilute systems, including the Mn4Ca cluster in the oxygen evolving complex of photosystem II.

Vanadium Alkylidyne Initiated Cyclic Polymer Synthesis: The Importance of a Deprotiovanadacyclobutadiene Moiety.

Reported is the catalytic cyclic polymer synthesis by a 3d transition metal complex: a V(V) alkylidyne, [(dBDI)V≡CtBu(OEt2)] (1-OEt2), supported by the deprotonated β-diketiminate dBDI2- (dBDI2- = ArNC(CH3)CHC(CH2)NAr, Ar = 2,6-iPr2C6H3). Complex 1-OEt2 is a precatalyst for the polymerization of phenylacetylene (PhCCH) to give cyclic poly(phenylacetylene) (c-PPA), whereas its precursor, complex [(BDI)V≡CtBu(OTf)] (2-OTf; BDI- = [ArNC(CH3)]2CH, Ar = 2,6-iPr2C6H3, OTf = OSO2CF3), and the zwitterion [((C6F5)3B-dBDI)V≡CtBu(OEt2)] (3-OEt2) exhibit low catalytic activity despite having a neopentylidyne ligand. Cyclic polymer topologies were verified by size-exclusion chromatography (SEC) and intrinsic viscosity studies. A component of the mechanism of the cyclic polymerization reaction was probed by isolation and full characterization of 4- and 6-membered metallacycles as model intermediates. Metallacyclobutadiene (MCBD) and deprotiometallacyclobutadiene (dMCBD) complexes (dBDI)V[C(tBu)C(H)C(tBu)] (4-tBu) and (BDI)V[C(tBu)CC(Mes)] (5-Mes), respectively, were synthesized upon reaction with bulkier alkynes, tBu- (tBuCCH) and Mes-acetylene (MesCCH), with 1-OEt2. Furthermore, the reaction of the conjugate acid of 1-OEt2, [(BDI)V≡CtBu(OTf)] (2-OTf), with the conjugated base of phenylacetylene, lithium phenylacetylide (LiCCPh), yields the doubly deprotio-metallacycle complex, [Li(THF)4]{(BDI)V[C(Ph)CC(tBu)CC(Ph)]} (6). Protonation of the doubly deprotio-metallacycle complex 6 yields 6-H+, a catalytically active species toward the polymerization of PhCCH, for which the polymers were also confirmed to be cyclic by SEC studies. Computational mechanistic studies complement the experimental observations and provide insight into the mechanism of cyclic polymer growth. The noninnocence of the supporting dBDI2- ligand and its role in proton shuttling to generate deprotiometallacyclobutadiene (dMCBD) complexes that proposedly culminate in the formation of catalytically active V(III) species are also discussed. This work demonstrates how a dMCBD moiety can react with terminal alkynes to form cyclic polyalkynes.

Recent Advances on the Development of Early Transition Metal Complexes for Photo‐Assisted Cytotoxicity Applications

AbstractFor targeted therapy, the strategic use of an inactive precursor or “prodrug” could be an attractive strategy. Photo‐assisted chemotherapy offers a smart opportunity for developing new inorganic prodrugs for selective and temporal regulation on the chemotherapeutic activity of the prodrugs with light. The 3d transition metal complexes with versatile coordination number and geometry, redox, thermodynamic and kinetic properties, the presence of low‐energy metal‐centered electronic transitions, and the ability to exhibit light‐assisted chemical reactions have emerged as strategic tools for photo‐chemotherapeutic applications. Transition metal complexes are typically characterized by metal‐centered, ligand to metal, metal to ligand or intra‐ligand electronic transitions, and photo‐activated electronic states of the transition metal complexes potentially exhibit a wide range of chemical reactions viz. intramolecular oxido‐reduction reactions, intramolecular rearrangements, ligand exchange reactions or energy transfer those cascades into the generation of ROS (⋅OH, O2−⋅, O22−, 1O2), small molecules like H2, N2, CO or NO, and alkyl or aryl radicals. Applications of photo‐activable transition metal complexes for generating cytotoxic ions or radicals in the presence of light have emerged as an attractive strategy for photo‐activated chemotherapy (PACT). Here in, we reviewed the photophysical and photochemical aspects of the early transition metal complexes exhibiting photo‐ activated chemotherapy.

Controlling the symmetry of hexamonodentate 3d-transition metal complexes through symmetry propagation from high-symmetry Ti-Mo and Zr-Mo clusters via hydrogen-bonding interactions.

The symmetry of one of the simplest hexamonodentate complexes, [M(H2O)6]2+ (M = Fe, Co, Ni, and Zn), was controlled by tuning interactions in the second coordination sphere. Highly symmetric Ti-Mo or Zr-Mo cluster cations acted as symmetry templates, imposing a crystallographic trigonal coordination geometry in the hexamonodentate complexes through intermolecular hydrogen-bonding interactions. Magnetic measurements revealed that the ideal trigonal symmetry results in weak spin-orbit coupling for high-spin FeII complexes, despite the T-term ground state in the octahedral geometry. In contrast, high-spin CoII analogues with the T-term ground state exhibited strong spin-orbit coupling. DFT studies supported that a d6 FeII ion in the D3 symmetry has a 5A1 ground state while a d7 CoII in the same symmetry has a 4E ground state. Single-ion magnet behavior was observed in the CoII complexes. These results demonstrate that incorporating a diamagnetic, highly symmetric cluster enables precise symmetry control in single-ion magnets containing only monodentate ligands.

Nickel(II) Phototheranostics: A Case Study in Photoactivated H2O2-Enhanced Immunotherapy.

Phototheranostics have emerged as a promising subset of cancer theranostics owing to their potential to provide precise photoinduced diagnoses and therapeutic outcomes. However, the design of phototheranostics remains challenging due to the nature of tumors and their microenvironment, including limitations to the oxygen supply, high rates of recurrence and metastasis, and the immunosuppressive state of cancer cells. Here we report a dual-functional oxygen-independent phototheranostic agent, Ni-2, rationally designed to provide a near-infrared (NIR) photoactivated thermal- and hydroxyl radical (•OH)-enhanced photoimmunotherapeutic anticancer response. Under 880 nm laser irradiation, Ni-2 exhibited high photostability and excellent photoacoustic and photothermal effects with a photothermal conversion efficacy of 58.0%, as well as novel photoredox features that allowed the catalytic conversion of H2O2 to •OH upon photooxidation of Ni(II) to Ni(III). As a multifunctional photoagent, Ni-2 was found not only to inhibit tumor growth in a CT26 tumor-bearing mouse model but also to activate an immune response via a combination of photothermal- and H2O2-induced effects. When combined with an antiprogrammed death-ligand 1 (aPD-L1), Ni-2 treatment allowed for the suppression of distant tumor growth and cancer metastasis. Collectively, the present results provide support for the proposition that Ni-2 or its analogues could emerge as useful tools for photoimmunotherapy. They also highlight the potential of appropriately designed 3d transition metal complexes as "all- in-one" phototheranostics.

Field-induced Co(II) single-ion magnet in octahedral [S6] coordination environment

The soft donor ligands are of great importance to the pursuit of 3d transition-metal complexes with large magnetic anisotropy. Herein, a soft tripodal ligand, hydrotris(mercaptobenzothiazolyl)borate (Tbz) was used to construct a high-spin mononuclear complex [CoII(Tbz)2] (1), having an octahedral geometry in an S6 donor set. The combination of direct-current (dc) magnetic susceptibility and Low-temperature high-field electron paramagnetic resonance (HFEPR) reveals the easy-axis magnetic anisotropy of 1. Complex 1 shows field-induced slow relaxation of magnetization at an applied magnetic field of 1000 Oe, indicating the behavior of single-molecule magnet. The foregoing result constitutes the first instance of Co(II)-based single-ion magnet containing a CoS6 unit.

DFT and TD-DFT calculations for electronic, magnetic, and optical characteristics of the 3d transition metal complexes for hexaazabipyH2

The electronic, magnetic, and optical characteristics of hexaazabipyH2 molecule (HA) and the 3d transition metal complexes for hexaazabipyH2 (TMHA) are investigated utilizing DFT and TD-DFT calculations. The stability of the investigated complexes is confirmed by the binding energy, molecular dynamic, and vibrational frequencies. The calculated HOMO-LUMO gap values show that the HA and TMHA are semiconductors. The magnetic moment (µ) for the investigated complexes is estimated, and the greatest µ value (3.76 µB) is recorded for the CrHA complex. The existence of the TM atom influences the UV–Vis spectrum of HA, where a redshift has occurred for the TMHA complexes except the ZnHA. The MnHAcomplex has a high light harvesting efficiency value of 0.403. The HA and TMHA complexes have refractive indices in the range of 2.311 to 3.323. Our results show that the HA as well TMHA complexes might be promising materials for solar cells and optoelectronics applications.

Spin-State Splittings in 3d Transition-Metal Complexes Revisited: Toward a Reliable Theory Benchmark

A new composite method for the calculation of spin-crossover energies in 3d transition-metal complexes based on multireference methods is presented. The method reduces to MRCISD+Q at the complete-basis-set (CBS) level for atomic ions, for which it gives excitation energies with a mean absolute error of only ca. 0.01 eV. For molecular complexes, the CASPT2+δMRCI composite approach corresponds to a CASPT2/CBS calculation augmented by a high-level MRCISD+Q-CASPT2 correction with a smaller ligand basis set. For a set of test complexes, the approach reproduces full MRCISD+Q/CBS results to within better than 0.04 eV, without depending on any arbitrary IPEA shifts. The high-quality CASPT2+δMRCI method has then been applied to a series of 3d transition-metal hexaqua complexes in aqueous solution, augmented by an elaborate 3D-RISM-SCF solvent treatment of the underlying structures. It provides unprecedented agreement with experiment for the lowest-lying vertical spin-flip excitation energies, except for the Fe3+ system. Closer examination of the latter case provides strong evidence that the observed lowest-energy excitation at 1.56 eV, which has been used frequently for evaluating quantum-chemical methods, does not arise from the iron(III) hexaqua complex in solution, but from its singly deprotonated counterpart, .

Synthesis, magnetic and electromagnetic wave absorption properties of planar anisotrop Y2Co17@SiO2 rare earth soft magnetic composites

Intermetallic complexes of rare-earth and 3d transition metals with core-shell structures are commonly employed as microwave absorbing materials due to their high saturation magnetizations and natural resonance in GHz. Hence, we synthesized Y2Co17 alloy via the co-precipitation reduction-diffusion technique, then coated the Y2Co17 magnetic powders with SiO2 to create Y2Co17@SiO2 core-shell structures. The formation of Y2Co17@SiO2/polyurethane (PU) at various volume fractions and their magnetic, electromagnetic properties were investigated using x-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, and vector network analyzer. The microwave absorption characteristics of Y2Co17@SiO2/PU were also investigated at various volume fractions. We not only investigate the zero-reflection conditions of the samples with different volume fractions, but also show that every absorber has a strong reflection loss value (RL ≤ −65.00 dB) and excellent microwave absorption properties with an average RL of Y2Co17@SiO2/PU being below −10 dB at 8 GHz–18 GHz under different thicknesses, showing that the enhancement of microwave absorption performance arises from the balance between permeability and permittivity of absorber.

Spin-State Splittings in 3d Transition-Metal Complexes Revisited: Benchmarking Approximate Methods for Adiabatic Spin-State Energy Differences in Fe(II) Complexes.

The CASPT2+δMRCI composite approach reported in a companion paper has been extended and used to provide high-quality reference data for a series of adiabatic spin gaps (defined as ΔE = Equintet - Esinglet) of [FeIIL6]2+ complexes (L = CNH, CO, NCH, NH3, H2O), either at nonrelativistic level or including scalar relativistic effects. These highly accurate data have been used to evaluate the performance of various more approximate methods. Coupled-cluster theory with singles, doubles, and perturbative triples, CCSD(T), is found to agree well with the new reference data for Werner-type complexes but exhibits larger underestimates by up to 70 kJ/mol for the π-acceptor ligands, due to appreciable static correlation in the low-spin states of these systems. Widely used domain-based local CCSD(T) calculations, DLPNO-CCSD(T), are shown to depend very sensitively on the cutoff values used to construct the localized domains, and standard values are not sufficient. A large number of density functional approximations have been evaluated against the new reference data. The B2PLYP double hybrid gives the smallest deviations, but several functionals from different rungs of the usual ladder hierarchy give mean absolute deviations below 20 kJ/mol. This includes the B97-D semilocal functional, the PBE0* global hybrid with 15% exact-exchange admixture, as well as the local hybrids LH07s-SVWN and LH07t-SVWN. Several further functionals achieve mean absolute errors below 30 kJ/mol (M06L-D4, SSB-D, B97-1-D4, LC-ωPBE-D4, LH12ct-SsirPW92-D4, LH12ct-SsifPW92-D4, LH14t-calPBE-D4, LHJ-HFcal-D4, and several further double hybrids) and thereby also still overall outperform CCSD(T) or uncorrected CASPT2. While exact-exchange admixture is a crucial factor in favoring high-spin states, the present evaluations confirm that other aspects can be important as well. A number of the better-performing functionals underestimate the spin gaps for the π-acceptor ligands but overestimate them for L = NH3, H2O. In contrast to a previous suggestion, non-self-consistent density functional theory (DFT) computations on top of Hartree-Fock orbitals are not a promising path to produce accurate spin gaps in such complexes.

Bimolecular reactivity of 3d metal-centered excited states (Cr, Mn, Fe, Co)

Metal-centered (MC) excited states (ESs) of 3d transition metal complexes (TMCs) often possess rather low energies so that these represent the lowest energy ESs. Additionally, MC states are often strongly distorted, hence they efficiently decay non-radiatively to the ground state. As bimolecular photoinduced electron transfer (PET) and energy transfer (EnT) processes require contact to the substrate, the metal confinement of the ES wavefunction of MC states makes these processes challenging. Consequently, MC states are considered less useful as compared to long-lived charge transfer states of higher energy with wavefunctions extending onto the ligands. Despite these supposed drawbacks, some classes of TMCs can successfully engage in bimolecular PET and EnT processes with MC states being the photoactive states. We discuss these initial examples of MC ES reactivity covering chromium, manganese, iron, and cobalt complexes with the aim to gain a deeper understanding of these processes and to identify the decisive key parameters. Finally, we present catalytic photoredox and energy transfer processes using photosensitizers with suitable MC ESs.

Systematic Variation of 3d Metals in a Redox-Innocent Ligand Environment: Structures, Electrochemical Properties and CO2 Activation

In the endeavor to close the anthropogenic carbon cycle and produce goods in a de-fossilized future, electrochemical carbon dioxide reduction constitutes a powerful tool.[1] Herein,3d transition metal complexes range among the most effective catalysts to overcome the kinetic barriers for CO2 activation.[2] In a recent literature review, we analyzed the main reaction pathways of homogeneously catalyzed CO2 electroreduction from an organometallic perspective and classified them into two mechanisms: (1) direct coordination of carbon dioxide to the metal center prior to activation and (2) formation of a metal hydride as the intermediate reactive to CO2.[3] Although properties of the metal center such as hydricity, or substrate (CO2) and product (CO, HCO2H...) binding affinity, are crucial regarding the mechanism and the ability of the complex to mediate CO2 reduction, systematic variations of the metal within an identical, redox-innocent ligand backbone remain scarcely investigated.In this study,[4] we report on the synthesis, structures, and electrochemistry of 3d transition metal complexes (M = Mn(I), Fe(II), Co(II), Ni(II), Cu(I) and Zn(II)) coordinated by a new redox-innocent PNP pincer ligand system (Figure 1). The ligand combines a large steric demand, partially shielding the metal center, with a high degree of aromaticity. With these features, the ligand only marginally interferes in the redox processes but still takes sufficient π-backbonding to stabilize low-valent metals.The coordination compounds derived thereof were analyzed by spectroscopic methods (e.g., NMR, EPR, and Mössbauer) as well as crystal X-Ray diffraction to determine their spatial and electronic structures. These findings served as the starting point for a further exploration of the electrochemical reduction of the complexes via cyclic voltammetry. While the Mn, Cu, and Zn complexes solely exhibit ligand reduction or decomposition processes, the distinct electrochemical waves found for the Fe, Co and Ni coordination compounds could be assigned to metal-centered reduction events from M(II) down to M(0).For both cobalt and nickel, the reductions appear to be accompanied by their chloride ligands being lost or exchanged with the acetonitrile solvent, a fact that we currently investigate[5] as these phenomena remain misjudged across many (CO2) electroreduction catalysts. In contrast to Co and Ni, Fe undergoes a more complex reduction pattern likely yielding a dimeric species.Despite their unequal reduction pathways, the evolution of the voltammograms of the complexes under CO2 atmosphere indicates an interaction of each of the complexes with the substrate molecule in their reduced metal states. The d10 Ni(0) species putatively forms an Aresta-type Ni-η2-CO2 complex, in which the electron transfer to the substrate through backbonding is insufficient to enable electrocatalytic activity. At contrast, CO2 binding at the d9 Co(0) intermediate likely leads to additional electron uptake and formation of a formal Co(I) metallacarboxylate complex able to promote turnover (Figure 2).Eventually, we related our findings to the few literature precedents that incorporate redox-innocent ligands. This assessment shows that beneficial characteristics in the electrochemical activation of CO2 by complexes based on redox-innocent ligands are an unsaturated coordination sphere (coordination number = 4 or 5) as well as a d7 to d9 configuration in the reduced oxidation state (+I or 0). The on-purpose design of complexes that simultaneously meet these three characteristics hence provides a promising strategy for catalyst development. In particular, dynamic structural and electronic changes under electrochemical conditions, such as the exchange of chlorido ligands with acetonitrile as faced in this study, must be controlled to ensure the primary operation of the metal centers in the desired catalytic manifold.

Cooperative C-H Bond Activation by a Low-Spin d6 Iron-Aluminum Complex.

The reactions of transition metal complexes underpin numerous synthetic processes and catalytic transformations. Typically, this reactivity involves the participation of empty and filled molecular orbitals centered on the transition metal. Kinetically stabilized species, such as octahedral low-spin d6 transition metal complexes, are not expected to participate directly in these reactions. However, novel approaches that exploit metal–ligand cooperativity offer an opportunity to challenge these preconceptions. Here, we show that inclusion of an aluminum-based ligand into the coordination sphere of neutral low-spin d6 iron complex leads to unexpected reactivity. Complexes featuring an unsupported Fe–Al bond are capable of the intermolecular C–H bond activation of pyridines. Mechanistic analysis suggests that C–H activation proceeds through a reductive deprotonation in which the two metal centers (Fe and Al) act like a frustrated Lewis pair. The key to this behavior is a ground state destabilization of the d6 iron complex, brought about by the inclusion of the electropositive aluminum-based ligand. These findings have immediate implications for the design of reagents and catalysts based on first-row transition metals.

3d Metal Complexes in T-shaped Geometry as a Gateway to Metalloradical Reactivity.

ConspectusLow-valent, low-coordinate 3d metal complexes represent a class of extraordinarily reactive compounds that can act as reagents and catalysts for challenging bond-activation reactions. The pursuit of these electron-deficient metal complexes in low oxidation states demands ancillary ligands capable of providing not only energetic stabilization but also sufficiently high steric bulk at the metal center. From this perspective, pincer ligands are particularly advantageous, as their prearranged, meridional coordination mode scaffolds the active center while the substituents of the peripheral donor atoms provide effective steric shielding for the coordination sphere. In a T-shaped geometry, the transition metal complexes possess a precisely defined vacant coordination site, which, combined with the often observed high-spin electron configuration, exhibits unusually high selectivity of these compounds with respect to one-electron redox chemistry. In light of the intractable reaction pathways typically observed with related electronically unsaturated 3d transition metal complexes, the pincer coordination mode enables the isolation of low-valent compounds with more controlled and unique reactivity. We have thus investigated a series of T-shaped metal(I) complexes using three different types of pincer ligands, which may be regarded as "metalloradicals" due to their selectively exposed unpaired electrons.These compounds display remarkably high thermal stability and represent rarely observed "naked" monovalent metal species featuring both monomeric and dimeric structures. Extensive reactivity studies using various organic substrates highlight a strong tendency of these paramagnetic compounds to undergo one-electron oxidation, leading to the isolation of a plethora of metal(II) species with reduced organic ligands as unusual structural elements. The exploration of C2 symmetric T-shaped Ni(I) complexes as asymmetric catalysts also shows success in enantioselective hydrodehalogenation of geminal dihalogenides. In addition, this specific class of low-valent, low-coordinate complexes can be further diversified by introducing redox-active pincer ligands or building homobimetallic systems with two T-shaped units.This Account focuses on the discussion of selected examples of iron, cobalt, and nickel pincer complexes bearing a [P,N,P] or [N,N,N] donor set; however, their electronic structure and radical-type reactivity can be broadly extended to other pincer systems. The availability of various types of pincer ligands should allow fine-tuning of the reactivity of the T-shaped complexes. Given the unprecedented reactivity observed with these compounds, we expect the studies of T-shaped 3d metal complexes to be a fertile field for advancing base metal catalysis.

Systematic Variation of 3d Metal Centers in a Redox-Innocent Ligand Environment: Structures, Electrochemical Properties, and Carbon Dioxide Activation.

Coordination compounds of earth-abundant 3d transition metals are among the most effective catalysts for the electrochemical reduction of carbon dioxide (CO2). While the properties of the metal center are crucial for the ability of the complexes to electrochemically activate CO2, systematic variations of the metal within an identical, redox-innocent ligand backbone remain insufficiently investigated. Here, we report on the synthesis, structural and spectroscopic characterization, and electrochemical investigation of a series of 3d transition-metal complexes [M = Mn(I), Fe(II), Co(II), Ni(II), Cu(I), and Zn(II)] coordinated by a new redox-innocent PNP pincer ligand system. Only the Fe, Co, and Ni complexes reveal distinct metal-centered electrochemical reductions from M(II) down to M(0) and show indications for interaction with CO2 in their reduced states. The Ni(0) d10 species associates with CO2 to form a putative Aresta-type Ni-η2-CO2 complex, where electron transfer to CO2 through back-bonding is insufficient to enable electrocatalytic activity. By contrast, the Co(0) d9 intermediate binding CO2 can undergo additional electron uptake into a formal cobalt(I) metallacarboxylate complex able to promote turnover. Our data, together with the few literature precedents, single out that an unsaturated coordination sphere (coordination number = 4 or 5) and a d7-to-d9 configuration in the reduced low oxidation state (+I or 0) are characteristics that foster electrochemical CO2 activation for complexes based on redox-innocent ligands.