PhenTAA: A Redox-Active N4-Macrocyclic Ligand Featuring Donor and Acceptor Moieties.

Here, we present the development and characterization of the novel PhenTAA macrocycle as well as a series of [Ni(R2PhenTAA)]n complexes featuring two sites for ligand-centered redox-activity. These differ in the substituent R (R = H, Me, or Ph) and overall charge of the complex n (n = -2, -1, 0, +1, or +2). Electrochemical and spectroscopic techniques (CV, UV/vis-SEC, X-band EPR) reveal that all redox events of the [Ni(R2PhenTAA)] complexes are ligand-based, with accessible ligand charges of -2, -1, 0, +1, and +2. The o-phenylenediamide (OPD) group functions as the electron donor, while the imine moieties act as electron acceptors. The flanking o-aminobenzaldimine groups delocalize spin density in both the oxidized and reduced ligand states. The reduced complexes have different stabilities depending on the substituent R. For R = H, dimerization occurs upon reduction, whereas for R = Me/Ph, the reduced imine groups are stabilized. This also gives electrochemical access to a [Ni(R2PhenTAA)]2- species. DFT and TD-DFT calculations corroborate these findings and further illustrate the unique donor-acceptor properties of the respective OPD and imine moieties. The novel [Ni(R2PhenTAA)] complexes exhibit up to five different ligand-based oxidation states and are electrochemically stable in a range from -2.4 to +1.8 V for the Me/Ph complexes (vs Fc/Fc+).

Dry reforming of methane over single-atom Rh/Al2O3 catalysts prepared by exsolution.

Single-atom catalysts often show exceptionally high performance per metal loading. However, the isolated atom sites tend to agglomerate during preparation and/or high-temperature reaction. Here we show that in the case of Rh/Al2O3 this deactivation can be prevented by dissolution/exsolution of metal atoms into/from the support. We design and synthesise a series of single-atom catalysts, characterise them and study the impact of exsolution in the dry reforming of methane at 700-900 °C. The catalysts' performance increases with increasing reaction time, as the rhodium atoms migrate from the subsurface to the surface. Although the oxidation state of rhodium changes from Rh(iii) to Rh(ii) or Rh(0) during catalysis, atom migration is the main factor affecting catalyst performance. The implications of these results for preparing real-life catalysts are discussed.

Combining metal-metal cooperativity, metal-ligand cooperativity and chemical non-innocence in diiron carbonyl complexes.

Several metalloenzymes, including [FeFe]-hydrogenase, employ cofactors wherein multiple metal atoms work together with surrounding ligands that mediate heterolytic and concerted proton-electron transfer (CPET) bond activation steps. Herein, we report a new dinucleating PNNP expanded pincer ligand, which can bind two low-valent iron atoms in close proximity to enable metal-metal cooperativity (MMC). In addition, reversible partial dearomatization of the ligand's naphthyridine core enables both heterolytic metal-ligand cooperativity (MLC) and chemical non-innocence through CPET steps. Thermochemical and computational studies show how a change in ligand binding mode can lower the bond dissociation free energy of ligand C(sp3)-H bonds by ∼25 kcal mol-1. H-atom abstraction enabled trapping of an unstable intermediate, which undergoes facile loss of two carbonyl ligands to form an unusual paramagnetic (S = ) complex containing a mixed-valent iron(0)-iron(i) core bound within a partially dearomatized PNNP ligand. Finally, cyclic voltammetry experiments showed that these diiron complexes show catalytic activity for the electrochemical hydrogen evolution reaction. This work presents the first example of a ligand system that enables MMC, heterolytic MLC and chemical non-innocence, thereby providing important insights and opportunities for the development of bimetallic systems that exploit these features to enable new (catalytic) reactivity.

Controlling Radical-Type Single-Electron Elementary Steps in Catalysis with Redox-Active Ligands and Substrates.

Advances in (spectroscopic) characterization of the unusual electronic structures of open-shell cobalt complexes bearing redox-active ligands, combined with detailed mapping of their reactivity, have uncovered several new catalytic radical-type protocols that make efficient use of the synergistic properties of redox-active ligands, redox-active substrates, and the metal to which they coordinate. In this perspective, we discuss the tools available to study, induce, and control catalytic radical-type reactions with redox-active ligands and/or substrates, contemplating recent developments in the field, including some noteworthy tools, methods, and reactions developed in our own group. The main topics covered are (i) tools to characterize redox-active ligands; (ii) novel synthetic applications of catalytic reactions that make use of redox-active carbene and nitrene substrates at open-shell cobalt-porphyrins; (iii) development of catalytic reactions that take advantage of purely ligand- and substrate-based redox processes, coupled to cobalt-centered spin-changing events in a synergistic manner; and (iv) utilization of redox-active ligands to influence the spin state of the metal. Redox-active ligands have emerged as useful tools to generate and control reactive metal-coordinated radicals, which give access to new synthetic methodologies and intricate (electronic) structures, some of which are yet to be exposed.

Di-tert-butyldiphosphatetrahedrane as a Source of 1,2-Diphosphacyclobutadiene Ligands.

Reactions of di-tert-butyldiphosphatetrahedrane (1) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations.

Revisiting the Electronic Structure of Cobalt Porphyrin Nitrene and Carbene Radicals with NEVPT2-CASSCF Calculations: Doublet versus Quartet Ground States.

Cobalt porphyrin complexes are established catalysts for carbene and nitrene radical group-transfer reactions. The key carbene and mono- and bisnitrene radical complexes coordinated to [Co(TPP)] (TPP = tetraphenylporphyrin) have previously been investigated with a variety of experimental techniques and supporting (single-reference) density functional theory (DFT) calculations that indicated doublet (S = 1/2) ground states for all three species. In this contribution, we revisit their electronic structures with multireference N-electron valence state perturbation theory (NEVPT2)-complete-active-space self-consistent-field (CASSCF) calculations to investigate possible multireference contributions to the ground-state wave functions. The carbene ([CoIII(TPP)(•CHCO2Et)]) and mononitrene ([CoIII(TPP)(•NNs)]) radical complexes were confirmed to have uncomplicated doublet ground states, although a higher carbene or nitrene radical character and a lower Co-C/N bond order was found in the NEVPT2-CASSCF calculations. Supported by electron paramagnetic resonance analysis and spin counting, paramagnetic molar susceptibility determination, and NEVPT2-CASSCF calculations, we report that the cobalt porphyrin bisnitrene complex ([CoIII(TPP•)(•NNs)2]) has a quartet (S = 3/2) spin ground state, with a thermally accesible multireference and multideterminant "broken-symmetry" doublet spin excited state. A spin flip on the porphyrin-centered unpaired electron allows for interconversion between the quartet and broken-symmetry doublet spin states, with an approximate 10-fold higher Boltzmann population of the quartet at room temperature.

Photo-Initiated Cobalt-Catalyzed Radical Olefin Hydrogenation.

Outer-sphere radical hydrogenation of olefins proceeds via stepwise hydrogen atom transfer (HAT) from transition metal hydride species to the substrate. Typical catalysts exhibit M-H bonds that are either too weak to efficiently activate H2 or too strong to reduce unactivated olefins. This contribution evaluates an alternative approach, that starts from a square-planar cobalt(II) hydride complex. Photoactivation results in Co-H bond homolysis. The three-coordinate cobalt(I) photoproduct binds H2 to give a dihydrogen complex, which is a strong hydrogen atom donor, enabling the stepwise hydrogenation of both styrenes and unactivated aliphatic olefins with H2 via HAT.

Catalytic Chemoselective Sulfimidation with an Electrophilic [CoIII (TAML)]- -Nitrene Radical Complex*.

The cobalt species PPh4 [CoIII (TAMLred )] is a competent and stable catalyst for the sulfimidation of (aryl)(alkyl)-substituted sulfides with iminoiodinanes, reaching turnover numbers up to 900 and turnover frequencies of 640 min-1 under mild and aerobic conditions. The sulfimidation proceeds in a highly chemoselective manner, even in the presence of alkenes or weak C-H bonds, as supported by inter- and intramolecular competition experiments. Functionalization of the sulfide substituent with various electron-donating and electron-withdrawing arenes and several alkyl, benzyl and vinyl fragments is tolerated, with up to quantitative product yields. Sulfimidation of phenyl allyl sulfide led to [2,3]-sigmatropic rearrangement of the initially formed sulfimide species to afford the corresponding N-allyl-S-phenyl-thiohydroxylamines as attractive products. Mechanistic studies suggest that the actual nitrene transfer to the sulfide proceeds via (previously characterized) electrophilic nitrene radical intermediates that afford the sulfimide products via electronically asynchronous transition states, in which SET from the sulfide to the nitrene radical complex precedes N-S bond formation in a single concerted process.

Low-Valence Anionic α-Diimine Iron Complexes: Synthesis, Characterization, and Catalytic Hydroboration Studies.

The synthesis of rare anionic heteroleptic and homoleptic α-diimine iron complexes is described. Heteroleptic BIAN (bis(aryl)iminoacenaphthene) complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] were synthesized by reduction of the [(BIAN)FeBr2] precursor complex using stoichiometric amounts of potassium graphite in the presence of the corresponding olefin. The electronic structure of these paramagnetic species was investigated by numerous spectroscopic analyses (NMR, EPR, 57Fe Mössbauer, UV-vis), magnetic measurements (Evans NMR method, SQUID), and theoretical techniques (DFT, CASSCF). Whereas anion 1 is a low-spin complex, anion 2 consists of an intermediate-spin Fe(III) center. Both complexes are efficient precatalysts for the hydroboration of carbonyl compounds under mild reaction conditions. The reaction of bis(anthracene) ferrate(1-) gave the homoleptic BIAN complex 3-[K([18]c-6)(thf)], which is less catalytically active. The electronic structure was elucidated with the same techniques as described for complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] and revealed an Fe(II) species in a quartet ground state.

Ligand-Mediated Spin-State Changes in a Cobalt-Dipyrrin-Bisphenol Complex.

The influence of a redox-active ligand on spin-changing events induced by the coordination of exogenous donors is investigated within the cobalt complex [CoII(DPP·2-)], bearing a redox-active DPP2- ligand (DPP = dipyrrin-bis(o,p-di-tert-butylphenolato) with a pentafluorophenyl moiety on the meso-position. This square-planar complex was subjected to the coordination of tetrahydrofuran (THF), pyridine, tBuNH2, and AdNH2 (Ad = 1-adamantyl), and the resulting complexes were analyzed with a variety of experimental (X-ray diffraction, NMR, UV-visible, high-resolution mass spectrometry, superconducting quantum interference device, Evans' method) and computational (density functional theory, NEVPT2-CASSCF) techniques to elucidate the respective structures, spin states, and orbital compositions of the corresponding octahedral bis-donor adducts, relative to [CoII(DPP·2-)]. This starting species is best described as an open-shell singlet complex containing a DPP·2- ligand radical that is antiferromagnetically coupled to a low-spin (S = 1/2) cobalt(II) center. The redox-active DPPn- ligand plays a crucial role in stabilizing this complex and in its facile conversion to the triplet THF adduct [CoII(DPP·2-)(THF)2] and closed-shell singlet pyridine and amine adducts [CoIII(DPP3-)(L)2] (L = py, tBuNH2, or AdNH2). Coordination of the weak donor THF to [CoII(DPP·2-)] changes the orbital overlap between the DPP·2- ligand radical π-orbitals and the cobalt(II) metalloradical d-orbitals, which results in a spin-flip to the triplet ground state without changing the oxidation states of the metal or DPP·2- ligand. In contrast, coordination of the stronger donors pyridine, tBuNH2, or AdNH2 induces metal-to-ligand single-electron transfer, resulting in the formation of low-spin (S = 0) cobalt(III) complexes [CoIII(DPP3-)(L)2] containing a fully reduced DPP3- ligand, thus explaining their closed-shell singlet electronic ground states.

Single-Electron Transfer in Frustrated Lewis Pair Chemistry.

Frustrated Lewis pairs (FLPs) are well known for their ability to activate small molecules. Recent reports of radical formation within such systems indicate single-electron transfer (SET) could play an important role in their chemistry. Herein, we investigate radical formation upon reacting FLP systems with dihydrogen, triphenyltin hydride, or tetrachloro-1,4-benzoquinone (TCQ) both experimentally and computationally to determine the nature of the single-electron transfer (SET) events; that is, being direct SET to B(C6 F5 )3 or not. The reactions of H2 and Ph3 SnH with archetypal P/B FLP systems do not proceed via a radical mechanism. In contrast, reaction with TCQ proceeds via SET, which is only feasible by Lewis acid coordination to the substrate. Furthermore, SET from the Lewis base to the Lewis acid-substrate adduct may be prevalent in other reported examples of radical FLP chemistry, which provides important design principles for radical main-group chemistry.

Aggregation and Degradation of White Phosphorus Mediated by N-Heterocyclic Carbene Nickel(0) Complexes.

The reaction of zerovalent nickel compounds with white phosphorus (P4 ) is a barely explored route to binary nickel phosphide clusters. Here, we show that coordinatively and electronically unsaturated N-heterocyclic carbene (NHC) nickel(0) complexes afford unusual cluster compounds with P1 , P3 , P5 and P8 units. Using [Ni(IMes)2 ] [IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene], electron-deficient Ni3 P4 and Ni3 P6 clusters have been isolated, which can be described as superhypercloso and hypercloso clusters according to the Wade-Mingos rules. Use of the bulkier NHC complexes [Ni(IPr)2 ] or [(IPr)Ni(η6 -toluene)] [IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] affords a closo-Ni3 P8 cluster. Inverse-sandwich complexes [(NHC)2 Ni2 P5 ] (NHC=IMes, IPr) with an aromatic cyclo-P5 - ligand were identified as additional products.

Photoinduced and Thermal Single-Electron Transfer to Generate Radicals from Frustrated Lewis Pairs.

Archetypal phosphine/borane frustrated Lewis pairs (FLPs) are famed for their ability to activate small molecules. The mechanism is generally believed to involve two-electron processes. However, the detection of radical intermediates indicates that single-electron transfer (SET) generating frustrated radical pairs could also play an important role. These highly reactive radical species typically have significantly higher energy than the FLP, which prompted this investigation into their formation. Herein, we provide evidence that the classical phosphine/borane combinations PMes3 /B(C6 F5 )3 and PtBu3 /B(C6 F5 )3 both form an electron donor-acceptor (charge-transfer) complex that undergoes visible-light-induced SET to form the corresponding highly reactive radical-ion pairs. Subsequently, we show that by tuning the properties of the Lewis acid/base pair, the energy required for SET can be reduced to become thermally accessible.

Electronically Asynchronous Transition States for C-N Bond Formation by Electrophilic [CoIII(TAML)]-Nitrene Radical Complexes Involving Substrate-to-Ligand Single-Electron Transfer and a Cobalt-Centered Spin Shuttle.

The oxidation state of the redox noninnocent tetra-amido macrocyclic ligand (TAML) scaffold was recently shown to affect the formation of nitrene radical species on cobalt(III) upon reaction with PhI=NNs [van Leest N. P.; J. Am. Chem. Soc.2020, 142, 552-563]. For the neutral [Co III (TAML sq )] complex, this leads to the doublet (S = 1/2) mono-nitrene radical species [Co III (TAML q )(N • Ns)(Y)] (bearing an unidentified sixth ligand Y in at least the frozen state), while a triplet (S = 1) bis-nitrene radical species [Co III (TAML q )(N • Ns) 2 ] - is generated from the anionic [Co III (TAML red )] - complex. The one-electron-reduced Fischer-type nitrene radicals (N•Ns-) are formed through single (mono-nitrene) or double (bis-nitrene) ligand-to-substrate single-electron transfer (SET). In this work, we describe the reactivity and mechanisms of these nitrene radical complexes in catalytic aziridination. We report that [Co III (TAML sq )] and [Co III (TAML red )] - are both effective catalysts for chemoselective (C=C versus C-H bonds) and diastereoselective aziridination of styrene derivatives, cyclohexane, and 1-hexene under mild and even aerobic (for [Co III (TAML red )] -) conditions. Experimental (Hammett plots; [Co III (TAML)]-nitrene radical formation and quantification under catalytic conditions; single-turnover experiments; and tests regarding catalyst decomposition, radical inhibition, and radical trapping) in combination with computational (density functional theory (DFT), N-electron valence state perturbation theory corrected complete active space self-consistent field (NEVPT2-CASSCF)) studies reveal that [Co III (TAML q )(N • Ns)(Y)], [Co III (TAML q )(N • Ns) 2 ] -, and [Co III (TAML sq )(N • Ns)] - are key electrophilic intermediates in aziridination reactions. Surprisingly, the electrophilic one-electron-reduced Fischer-type nitrene radicals do not react as would be expected for nitrene radicals (i.e., via radical addition and radical rebound). Instead, nitrene transfer proceeds through unusual electronically asynchronous transition states, in which the (partial) styrene substrate to TAML ligand (single-) electron transfer precedes C-N coupling. The actual C-N bond formation processes are best described as involving a nucleophilic attack of the nitrene (radical) lone pair at the thus (partially) formed styrene radical cation. These processes are coupled to TAML-to-cobalt and cobalt-to-nitrene single-electron transfer, effectively leading to the formation of an amido-γ-benzyl radical (NsN--CH2-•CH-Ph) bound to an intermediate spin (S = 1) cobalt(III) center. Hence, the TAML moiety can be regarded to act as a transient electron acceptor, the cobalt center behaves as a spin shuttle, and the nitrene radical acts as a nucleophile. Such a mechanism was hitherto unknown for cobalt-catalyzed hypovalent group transfer and the more general transition-metal-catalyzed nitrene transfer to alkenes but is now shown to complement the known concerted and stepwise mechanisms for N-group transfer.

Ligand Redox Noninnocence in [CoIII(TAML)]0/- Complexes Affects Nitrene Formation.

The redox noninnocence of the TAML scaffold in cobalt-TAML (tetra-amido macrocyclic ligand) complexes has been under debate since 2006. In this work, we demonstrate with a variety of spectroscopic measurements that the TAML backbone in the anionic complex [CoIII(TAMLred)]- is truly redox noninnocent and that one-electron oxidation affords [CoIII(TAMLsq)]. Multireference (CASSCF) calculations show that the electronic structure of [CoIII(TAMLsq)] is best described as an intermediate spin (S = 1) cobalt(III) center that is antiferromagnetically coupled to a ligand-centered radical, affording an overall doublet (S = 1/2) ground-state. Reaction of the cobalt(III)-TAML complexes with PhINNs as a nitrene precursor leads to TAML-centered oxidation and produces nitrene radical complexes without oxidation of the metal ion. The ligand redox state (TAMLred or TAMLsq) determines whether mono- or bis-nitrene radical complexes are formed. Reaction of [CoIII(TAMLsq)] or [CoIII(TAMLred)]- with PhINNs results in the formation of [CoIII(TAMLq)(N•Ns)] and [CoIII(TAMLq)(N•Ns)2]-, respectively. Herein, ligand-to-substrate single-electron transfer results in one-electron-reduced Fischer-type nitrene radicals (N•Ns-) that are intermediates in catalytic nitrene transfer to styrene. These nitrene radical species were characterized by EPR, XANES, and UV-vis spectroscopy, high-resolution mass spectrometry, magnetic moment measurements, and supporting CASSCF calculations.

Direct synthesis of an anionic 13-vertex closo-cobaltacarborane cluster.

Reaction of 1,2-bis(diphenylphosphino)-ortho-carborane (L) with [K(thf){(MesBIAN)Co(η4-cod)}] (1, MesBIAN = bis(mesityliminoace-naphthene)diimine, cod = 1,5-cyclooctadiene) affords an anionic 13-vertex closo-cobaltacarborane cluster (2) in one step. The mechanism of this transformation has been studied by experimental and quantum chemical techniques, which suggest that a series of outer-sphere electron transfer and isomerisation processes occurs. This work shows that low-valent metalate anions are promising reagents for the synthesis of anionic metallacarborane clusters.

A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones.

The dinuclear ruthenium complex [Ru2H(µ-H)(Me2dad)(dbcot)2] contains a 1,4-dimethyl-diazabuta-1,3-diene (Me2dad) as a non-innocent bridging ligand between the metal centers to give a [Ru2(Me2dad)] core. In addition, each ruthenium is bound to one dibenzo[a,e]cyclooctatetraene (dbcot) ligand. This Ru dimer converts H2 to protons and electrons. It also catalyzes reversibly under mild conditions the selective hydrogenation of vitamins K2 and K3 to their corresponding hydroquinone equivalents without affecting the C[double bond, length as m-dash]C double bonds. Mechanistic studies suggest that the [Ru2(Me2dad)] moiety, like hydrogenases, reacts with H2 and releases electrons and protons stepwise.

Uncatalyzed Oxidative C-H Amination of 9,10-Dihydro-9-Heteroanthracenes: A Mechanistic Study.

A new method for the one-step C-H amination of xanthene and thioxanthene with sulfonamides is reported, without the need for any metal catalyst. A benzoquinone was employed as a hydride (or two-electron and one-proton) acceptor. Moreover, a previously unknown and uncatalyzed reaction between iminoiodanes and xanthene, thioxanthene and dihydroacridines (9,10-dihydro-9-heteroanthracenes or dihydroheteroanthracenes) is disclosed. The reactions proceed through hydride transfer from the heteroarene substrate to the iminoiodane or benzoquinone, followed by conjugate addition of the sulfonamide to the oxidized heteroaromatic compounds. These findings may have important mechanistic implications for metal-catalyzed C-H amination processes involving nitrene transfer from iminoiodanes to dihydroheteroanthracenes. Due to the weak C-H bond, xanthene is an often-employed substrate in mechanistic studies of C-H amination reactions, which are generally proposed to proceed via metal-catalyzed nitrene insertion, especially for reactions involving nitrene or imido complexes that are less reactive (i.e., less strongly oxidizing). However, these substrates clearly undergo non-catalyzed (proton-coupled) redox coupling with amines, thus providing alternative pathways to the widely assumed metal-catalyzed pathways.

Aryldiazonium Salts as Nitrogen-Based Lewis Acids: Facile Synthesis of Tuneable Azophosphonium Salts.

Inspired by the commercially available azoimidazolium dyes (e.g., Basic Red 51) that can be obtained from aryldiazonium salts and N-heterocyclic carbenes, we developed the synthesis of a unique set of arylazophosphonium salts. A range of colours were obtained by applying readily tuneable phosphine donor ligands and para-substituted aryldiazonium salts as nitrogen-based Lewis acids. With cyclic voltammetry, a general procedure was designed to establish whether the reaction between a Lewis acid and a Lewis base occurs by single-electron transfer or electron-pair transfer.

Redox-Active Bis(phenolate) N-Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States.

A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate complexes are best formulated as Co(II) centers bound to closed-shell [OCO]2- dianions, of the general formula [(OCO)CoIIL] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms of the [(OCO)CoIIL] complexes reveal three oxidations accessible at potentials below 1.2 V vs Fc+/Fc, corresponding to generation of formally Co(V) species, but the true physical/spectroscopic oxidation states are much lower. Chemical oxidations afford the mono- and dications of the imidazoline NHC-derived complex, which were examined by computational and magnetic and spectroscopic methods, including single-crystal X-ray diffraction. The metal and ligand oxidation states of the monocationic complex are ambiguous; data are consistent with formulation as either [(SOCO)CoIII(THF)2]+ containing a closed-shell [SOCO]2- diphenolate ligand bound to a S = 1 Co(III) center, or [(SOCO•)CoII(THF)2]+ with a low-spin Co(II) ion ferromagnetically coupled to monoanionic [SOCO•]- containing a single unpaired electron distributed across the [OCO] framework. The dication is best described as [(SOCO0)CoII(THF)3]2+, with a single unpaired electron localized on the d7 Co(II) center and a doubly oxidized, charge-neutral, closed-shell SOCO0 ligand. The combined data provide for the first time unequivocal and structural evidence for [OCO] ligand redox activity. Notably, varying the degree of unsaturation in the NHC backbone shifts the ligand-based oxidation potentials by up to 400 mV. The possible chemical origins of this unexpected shift, along with the potential utility of the [OCO] pincer ligands for base-metal-mediated organometallic coupling catalysis, are discussed.