Non-innocent Ligand Research Articles

Diradicals as Topological Charge Carriers in Metal-Organic Toy Model Pt3(HIB)2.

We explore the eclipsed stacking of a metal-organic Kagome lattice containing heavy-metal nodes. Our model is Pt3(HIB)2, a hypothetical but viable member of a well-known family of hexaaminobenzene based metal-organic frameworks (MOFs). Applying space group theory, it is shown how molecular diradicals, brought into play by a noninnocent ligand, become topologically nontrivial bands when moving in a periodic potential. Three factors are required to enable this: (1) eclipsed stacking, which shifts the Fermi level near a symmetry-protected band crossing (2) the emergence of an electride-like band that renders the topological invariant equal to 1, thus nontrivial, and (3) Pt-induced spin-orbit coupling, to turn the crossing into a bulk band gap. The electride band, with its unforeseen role, bears kinship to the interlayer band in hexagonal superconductors. It places its charge density in the voids of the crystal, rather than around the atomic nuclei, and we name it a "pore band". While the synthesis of truly conductive MOFs has proven challenging, the analysis shows that intrinsically nonlocal physics may emerge from tunable molecular building blocks. With the richness of redox-active MOF chemistry, this offers a pathway to tailored topological electronics.

Synthesis and reactivity of a heteroleptic magnesium hydride on a dearomatized picolyl-based NNN-chelator.

Heteroleptic magnesium hydrides are important for their stoichiometric and catalytic reduction chemistry. Their primary nucleophilic site is typically the hydride, while the ancillary ligands commonly used are mostly spectators. Chemically non-innocent ligands in comparison are rarely applied on MgH as their reactivity can be complex. Milstein et al. have recently reported Mg-mediated alkyne hydrogenation by using their metal-ligand cooperation (MLC) concept on a dearomatized picolyl-based PNP pincer that is non-innocent with a nucleophilic nature. A '(PNP)MgH' is noted as the active catalyst in hydrogenation but without structural validation. Inspired by the same, we report herein a novel NNN-chelator (MesL) with a dearomatized picolyl moiety and its well-defined MgH. Having two prominent nucleophilic sites, the present MgH shows metal-ligand competition while reacting with certain electrophiles. It also distinguishes nonpolar alkynes and polar carbonyls by cleanly inserting itself into the former but not the latter. The nucleophilicities of the two sites are also probed by DFT methods and compared with Milstein's (PNP)MgH. Although the present system shows no MLC-type H2 activation, the addition of a CS2 molecule in that way is realized.

Comparative Electrocatalysis of Hydrogen Production and Oxidation: Technetium versus Rhenium Tris(thiolate) Complexes

AbstractThe development of an efficient catalyst that can selectively activate and generate hydrogen molecules is in urgent demand. Inspired by the 5d rhenium‐tris(thiolate) complex that is capable of catalytically producing and oxidizing H2, the mechanisms of electrocatalytic H2 oxidation (HOR) and evolution (HER) catalyzed by the 4d technetium‐tri(thiolate) analogs, and [TcL3] (L = diphenylphosphinobenzenethiolate, a noninnocent ligand), were investigated by DFT calculations, aiming at elucidating the role of the metal in metal‐ligand cooperativity. DFT calculations anticipate high reactivity in both HOR and HER for [TcL3] beyond that of its Re counterparts. Substituting the Re metal for Tc in metal‐tris(thiolate) complexes results in a greater thiyl‐radical character in the Tc complex compared to that in Re. Even when both complexes evolve H2 with similar [ECEC] mechanisms, the proton relays behave with a distinct disparity, featuring the S ligand in the Tc species as compared to the metal‐hydride in Re. The HOR mechanism also bifurcates as [TcL3]2+ is predicted to mainly occur via the ligand‐based pathway, in contrast to the predominant metal and ligand‐based reactivity for Re. This study established the role of the metal in HER and HOR while emphasizing the utility of such metal‐DPPBT cooperativity in the catalytic process.

Synthesis of a potassium capped terminal cobalt-oxido complex.

An unusual example of a potassium capped terminal cobalt-oxido complex has been isolated and crystallographically characterized. The synthesis of [tBu,TolDHP]CoOK proceeds from a previously reported parent compound, [tBu,TolDHP]CoOH, via deprotonation with KOtBu. Structural and electronic characterization suggest a weakly coupled dimer in a distinct seesaw geometry with a Co(III) oxidation state and a non-innocent radical ligand.

Ligand Noninnocence in β-Diketiminate and β-Diketimine Copper Complexes.

Metal-ligand cooperative systems have a long precedent in catalysis, with the classification depending on the site of substrate bond cleavage and formation and on redox state changes. Recently, our group reported the participation of a β-diketiminate ligand in chemical bonding to heterocumulenes such as CO2 and CS2 by tricopper complexes, leading to cooperative catalysis. Herein, we report the reactivity of these copper clusters, [Cu3EL]- (E = S, Se; L = tris(β-diketiminate) cyclophane ligand), toward other electrophiles, viz. alkyl halides and Brønsted acids. We identified a family of ligand-functionalized complexes, Cu3EL (R) (R = primary alkyls), and a series of disubstituted products, Cu3EL (R)2, through single-crystal X-ray diffraction, mass spectrometry, and infrared and UV-visible spectroscopy. As part of mechanistic studies on these alkylation reactions, we evaluated the acid-base reactivity of these complexes and the influence of the backbone substitution on the reduction potential. Implications of these findings for ligand noninnocence and the relevance of the metal core as a cofactor for the ligand's reactivity are discussed.

Role of non-redox innocent ligand units in the oxidation of alcohols with H2O2 catalyzed by μ-oxido-diiron(III) bis-phenolato polypyridyl complexes

Redox non-innocent ligands hold the potential to expand the redox chemistry and activity of transition metal catalysts. The impact of the additional redox chemistry of phenol ligands in oxidation catalysis is explored here in the complex μ-oxido-diiron(III) polypyridyl (1) [(L)Fe(III)(μ–O)Fe(III)(L)](ClO4)2 (where HL is 2-(((di(pyridin-2-yl)methyl) (pyridin-2-ylmethyl) amino)methyl)phenol) and its tert-butyl substituted analog 2, in which each of the Fe(III) centers is coordinated to a phenolato moiety of the ligand. Complex 1 was shown earlier to catalyse the oxidation of benzyl alcohols to aldehydes with H2O2. In particular acid was found to accelerate the reactions by removal of a lag period before catalysis initiated. Here, we use reaction monitoring with resonance Raman, UV/vis absorption and EPR spectroscopy to show that under catalytic conditions, i.e. with excess H2O2, rapid (< 5 s) loss of the phenolato moiety occurs, resulting in the formation of an N4 ligated Fe(III) complex. This N4 coordinated complex forms a Fe(III)-OOH species, which is responsible for alcohol oxidation and over time a relatively stable oxido-bridged dinuclear Fe(III) complex forms as a resting state in the catalytic system. The main role of acid in the catalysis is shown to be to facilitate the initial coordination of H2O2 by driving the formation of mononuclear complexes from 1 and 2. The data show that although the phenolato moiety imparts interesting redox properties on complex 1, it does not contribute directly to the oxidation catalysis observed with H2O2.

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

Exploring the Cooperation of the Redox Non-Innocent Ligand and Di-Cobalt Center for the Water Oxidation Reaction Catalyzed by a Binuclear Complex.

Water oxidation is a crucial reaction in the artificial photosynthesis system. In the present work, density functional calculations were employed to decipher the mechanism of water oxidation catalyzed by a binuclear cobalt complex, which was disclosed to be a homogeneous water oxidation catalyst in pH=7 phosphate buffer. The calculations showed that the catalytic cycle starts from the CoIII,III-OH2 species. Then, a proton-coupled electron transfer followed by a one-electron transfer process leads to the generation of the formal CoIV,IV-OH intermediate. The subsequent PCET produces the active species, namely the formal CoIV,V=O intermediate (4). The oxidation processes mainly occur on the ligand moiety, including the coordinated water moiety, implying a redox non-innocent behavior. Two cobalt centers keep their oxidation states and provide one catalytic center for water activation during the oxidation process. 4 triggers the O-O bond formation via the water nucleophilic attack pathway, in which the phosphate buffer ion functions as the proton acceptor. The O-O bond formation is the rate-limiting step with a calculated total barrier of 17.7 kcal/mol. The last electron oxidation process coupled with an intramolecular electron transfer results in the generation of O2.

Ruthenium(II) Polypyridyl Complexes with Benzoxazole Derivatives and Non-Innocent Ligands as Effective Antioxidants in Human Neuroblasts.

Ruthenium(II) polypyridyl complexes continue to raise increasing interest for the encouraging results in several biomedical areas. Considering their vast chemical-physical repertoire, in particular the possibility to switch from the sensitization of reactive oxygen species (ROS) to ROS-scavenging abilities by tuning the nature of their ligands, it is therefore surprising that their potential as antioxidants has not been largely investigated so far. Herein, we explored the antioxidant behaviour of the novel ruthenium compound [Ru(dbpy)(2,3-DAN)Cl]PF6 (Ru1), featuring a benzoxazole derivative (dpby=2,6-bis(4-methyl-2-benzoxazolyl)pyridine) and the non-innocent 2,3-diamminonaftalene (2,3-DAN) ligand, along with the reference tpy-containing analogue [Ru(tpy)(2,3-DAN)Cl]PF6 (Ru2) (tpy=2,2':6',2''-terpyridine). Following the synthesis and the electrochemical characterization, chemical antioxidant assays highlighted the beneficial role of dpby for the ROS-scavenging properties of Ru1. These data have been corroborated by the highest protective effect of Ru1 against the oxidative stress induced in SH-SY5Y human neuroblastoma, which exerts pro-survival and anti-inflammatory actions. The results herein reported highlight the potential of Ru1 as pharmacological tool in neurodegenerative diseases and specially prove that the antioxidant properties of such compounds are likely the result of a non-trivial synergetic action involving the bioactive ligands in their chemical architectures.

DFT Struggles to Predict the Energy Landscape for Iron Pyridine Diimine-Catalyzed [2 + 2] Cycloaddition of Alkenes: Insights into the Problem and Alternative Solutions.

In recent years, noninnocent pyridine diimine (PDI) complexes featuring first-row transition metals have emerged as prominent catalysts, demonstrating efficacy in a diverse range of vital organometallic transformations. However, the inherent complexity of the fundamental reactivity paradigm in these systems arises from the presence of a noninnocent ligand and the multispin feasibility of 3d metals. While density functional theory (DFT) has been widely used to unravel mechanistic insights, its limitations as a single-reference method can potentially misrepresent spin-state energetics, compromising our understanding of these intricate systems. In this study, we employ extensive high-level ab initio state averaged-complete active space self-consistent field/N-electron valence state perturbation theory (SA-CASSCF/NEVPT2) calculations in combination with DFT to investigate an iron-PDI-catalyzed [2 + 2] cycloaddition reaction of alkenes. The transformation proceeds through two major steps: oxidative cyclization and reductive elimination. Contrary to the predictions of DFT calculations, which suggest two-state reactivity in the reaction and identify reductive elimination as the turnover-limiting step, SA-CASSCF/NEVPT2-corrected results unequivocally establish a single-state reactivity scenario with oxidative cyclization as the turnover-limiting step. SA-CASSCF/NEVPT2-based insights into electronic ground states and electron distribution elucidate the intriguing interactions between the PDI ligand and the iron center, revealing the highly multiconfigurational nature of these species and providing a precise depiction of metal-ligand cooperativity throughout the transformation. A comparative assessment of several widely recognized DFT functionals against SA-CASSCF/NEVPT2-corrected data indicates that single-point energy calculations using the modern density functional MN15 on TPSSh geometries offer the most reliable density functional methodology, in scenarios where SA-CASSCF/NEVPT2 computational cost is a consideration.

Expanding the Scope of Aluminum Chemistry with Noninnocent Ligands.

ConspectusAluminum is the most abundant metal in the earth's crust at 8%, and it is also widely available domestically in many countries worldwide, which ensures a stable supply chain. To further the applications of aluminum (Al), such as in catalysis and electronic and energy storage materials, there has been significant interest in the synthesis and characterization of new Al coordination compounds that can support electron transfer (ET) and proton transfer (PT) chemistry. This has been achieved using redox and chemically noninnocent ligands (NILs) combined with the highly stable M(III) oxidation state of Al and in some cases the heavier group 13 ions, Ga and In.When ligands participate in redox chemistry or facilitate the breaking or making of new bonds, they are often termed redox or chemically noninnocent, respectively. Al(III) in particular supports rich ligand-based redox chemistry because it is so redox inert and will support the ligand across many charge and protonation states without entering into the reaction chemistry. To a lesser extent, we have reported on the heavier group 13 elements Ga and In, and this chemistry will also be included in this Account, where available.This Account is arranged into two technical sections, which are (1) Structures of Al-NIL complexes and (2) Reactivity of Al-NIL complexes. Highlights of the research work include reversible redox chemistry that has been enabled by ligand design to shut down radical coupling pathways and to prevent loss of H2 from unsaturated ligand sites. These reversible redox properties have in turn enabled the characterization of Class III electron delocalization through Al when two NIL are bound to the Al(III) in different charge states. Characterization of the metalloaromatic character of square planar Al and Ga complexes has been achieved, and characterization of the delocalized electronic structures has provided a model within which to understand and predict the ET and PT chemistry of the NIL group 13 compounds. The capacity of Al-NIL complexes to perform ET and PT has been employed in reactions that use ET or PT reactivity only or in reactions where coupled ET/PT affords hydride transfer chemistry. As an example, ligand-based PT reactions initiate metal-ligand cooperative bond activation pathways for catalysis: this includes acceptorless dehydrogenation of formic acid and anilines and transfer hydrogenation chemistry. In a complementary approach, ligand based ET/PT chemistry has been used in the study of dihydropyridinate (DHP-) chemistry where it was shown that N-coordination of group 13 ions lowers kinetic barriers to DHP- formation. Taken together, the discussion presented herein illustrates that the NIL chemistry of Al(III), and also of Ga(III) and In(III) holds promise for further developments in catalysis and energy storage.

Visible-Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity.

We report on the synthesis and characterization of a series of (mostly) air-stable diorganyl bis(pyridylimino) isoindolide (BPI) aluminum complexes and their chemistry upon visible-light excitation. The redox non-innocent BPI pincer ligand allows for efficient charge transfer homolytic processes of the title compounds. This makes them a universal platform for the generation of carbon-centered radicals. The photo-induced homolytic cleavage of the Al-C bonds was investigated by means of stationary and transient UV/Vis spectroscopy, spin trapping experiments, as well as EPR and NMR spectroscopy. The experimental findings were supported by quantum chemical calculations. Reactivity studies enabled the utilization of the aluminum complexes as reactants in tin-free Giese-type reactions and carbonyl alkylations under ambient conditions, which both indicated radical-polar crossover behavior. A deeper understanding of the physical fundamentals and photochemical process was provided, furnishing in turn a new strategy to control the reactivity of bench-stable aluminum organometallics.

IZCp and PZCp: Redox Non-innocent Cyclopentadienyl Ligands as Electron Reservoirs for Sandwich Complexes.

A long-sustained effort of systematic steric and electronic modification of cyclopentadienyl (Cp) ligands has enabled them to find wide-ranging, valuable applications. Herein, we present two novel Cp ligands: imidazolium- and pyrrolinium-substituted zwitterionic Cps (IZCp and PZCp), whose key utility is redox non-innocence─the ability to participate cooperatively with the metal center in redox reactions. Through the simple metalation of ZCps, the Cr(0) and Mo(0) half-sandwich complexes (IZCp)Cr(CO)3, (PZCp)Cr(CO)3, (IZCp)Mo(CO)3, and (PZCp)Mo(CO)3, respectively, as well as the Ru(II) sandwich complexes [(IZCp)RuCp]PF6 and [(PZCp)RuCp]PF6 were prepared. The sandwich complexes were fully characterized and showed by cyclic voltammetry reversible one-electron reduction at E1/2 potentials ranging from -1.7 to -2.7 V vs Fc/Fc+. These values are unusually low and have not been observed with other Cp ligands due to the instability of the reduced complexes. Density functional theory (DFT) calculations for the reduced sandwich derivatives with IZCp and PZCp showed their spin densities to be highly delocalized over their ZCp ligand moieties (70-90%). Electron paramagnetic resonance (EPR) analysis of the isolated K[(PZCp)Mo(CO)3] and (PZCp)RuCp also indicated a high degree of ligand-localized radical character. Thus, the IZCp and PZCp ligands act as electron reservoirs to sustain these sandwich complexes in highly reduced states. At the same time, the CO stretching frequencies of K[(PZCp)Mo(CO)3]: νCO 1871, 1748, and 1699 cm-1, rank the [PZCp]- ligand as the strongest electron-donating Cp ligand among the reported CpMo(CO)3 derivatives, whose νCO > 1746 cm-1. In addition, these redox non-innocent Cps were obtained in high yields and found to be practically air- and moisture-stable, unlike typical Cps.

Metal Complexes of Redox Non-Innocent Ligand N,N'-Bis(3,5-di-tertbutyl-2-hydroxy-phenyl)-1,2-phenylenediamine.

Redox non-innocent ligands react with metal precursors to form complexes where the oxidation states of the ligand and thus the metal atom cannot be easily defined. A well-known example of such ligands is bis(o-aminophenol) N,N'-bis(3,5-di-tertbutyl-2-hydroxy-phenyl)-1,2-phenylenediamine, previously developed by the Wieghardt group, which has a potentially tetradentate coordination mode and four distinct protonation states, whereas its electrochemical behavior allows for five distinct oxidation states. This rich redox chemistry, as well as the ability to coordinate to various transition metals, has been utilized in the syntheses of metal complexes with M2L, ML and ML2 stoichiometries, sometimes supported with other ligands. Different oxidation states of the ligand can adopt different coordination modes. For example, in the fully oxidized form, two N donors are sp2-hybridized, which makes the ligand planar, whereas in the fully reduced form, the sp3-hybridized N donors allow the formation of more flexible chelate structures. In general, the metal can be reduced during complexation, but redox processes of the isolated complexes typically occur on the ligand. Combination of this non-innocent ligand with redox-active transition metals may lead to complexes with interesting magnetic, electrochemical, photonic and catalytic properties.

Impact of the Methylene Bridge Substitution in Chelating NHC-Phosphine Mn(I) Catalyst for Ketone Hydrogenation.

Systematic modification of the chelating NHC-phosphine ligand (NHC = N-heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac-[(Ph2 PCH2 NHC)Mn(CO)3 Br] has been performed and the catalytic activity of the resulting complexes was evaluated using acetophenone as a benchmark substrate. While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by ca. 3 times providing maximal TON values in the range of 15000-20000. Mechanistic investigation combining experimental and computational studies allowed to rationalize this beneficial effect as an enhanced stabilization of reaction intermediates including anionic hydride species fac-[(Ph2 PC(Ph)NHC)Mn(CO)3 H]- playing a crucial role in the hydrogenation process. These results highlight the interest of such carbon bridge substitution strategy being rarely employed in the design of chemically non-innocent ligands.

Selective Cobalt-Mediated Formation of Hydrogen Peroxide from Water under Mild Conditions via Ligand Redox Non-Innocence.

Despite the broad importance of hydrogen peroxide (H2O2) in oxidative transformations, there are comparatively few viable routes for its production. The majority of commercial H2O2 is currently produced by the stepwise reduction of dioxygen (O2) via the anthraquinone process, but direct electrochemical formation from water (H2O) would have several advantages─namely, avoiding flammable gases or stepwise separations. However, the selective oxidation of H2O to form H2O2 over the thermodynamically favored product of O2 is a difficult synthetic challenge. Here, we present a molecular H2O oxidation system with excellent selectivity for H2O2 that functions both stoichiometrically and catalytically. We observe high efficiency for electrocatalytic H2O2 production at low overpotential with no O2 observed under any conditions. Mechanistic studies with both calculations and kinetic analyses from isolated intermediates suggest that H2O2 formation occurs in a bimolecular fashion via a dinuclear H2O2-bridged intermediate with an important role for a redox non-innocent ligand. This system showcases the ability of metal-ligand cooperativity and strategic design of the secondary coordination sphere to promote kinetically and thermodynamically challenging selectivity in oxidative catalysis.

Coordination-induced O-H/N-H bond weakening by a redox non-innocent, aluminum-containing radical

Several renewable energy schemes aim to use the chemical bonds in abundant molecules like water and ammonia as energy reservoirs. Because the O-H and N-H bonds are quite strong (>100 kcal/mol), it is necessary to identify substances that dramatically weaken these bonds to facilitate proton-coupled electron transfer processes required for energy conversion. Usually this is accomplished through coordination-induced bond weakening by redox-active metals. However, coordination-induced bond weakening is difficult with earth’s most abundant metal, aluminum, because of its redox inertness under mild conditions. Here, we report a system that uses aluminum with a redox non-innocent ligand to achieve significant levels of coordination-induced bond weakening of O-H and N-H bonds. The multisite proton-coupled electron transfer manifold described here points to redox non-innocent ligands as a design element to open coordination-induced bond weakening chemistry to more elements in the periodic table.

Electronic Structure and Transformation of Dinitrosyl Iron Complexes (DNICs) Regulated by Redox Non-Innocent Imino-Substituted Phenoxide Ligand.

The coupled NO-vibrational peaks [IR νNO 1775 s, 1716 vs, 1668 vs cm-1 (THF)] between two adjacent [Fe(NO)2] groups implicate the electron delocalization nature of the singly O-phenoxide-bridged dinuclear dinitrosyliron complex (DNIC) [Fe(NO)2(μ-ON2Me)Fe(NO)2] (1). Electronic interplay between [Fe(NO)2] units and [ON2Me]- ligand in DNIC 1 rationalizes that "hard" O-phenoxide moiety polarizes iron center(s) of [Fe(NO)2] unit(s) to enforce a "constrained" π-conjugation system acting as an electron reservoir to bestow the spin-frustrated {Fe(NO)2}9-{Fe(NO)2}9-[·ON2Me]2- electron configuration (Stotal = 1/2). This system plays a crucial role in facilitating the ligand-based redox interconversion, working in harmony to control the storage and redox-triggered transport of the [Fe(NO)2]10 unit, while preserving the {Fe(NO)2}9 core in DNICs {Fe(NO)2}9-[·ON2Me]2- [K-18-crown-6-ether)][(ON2Me)Fe(NO)2] (2) and {Fe(NO)2}9-[·ON2Me] [(ON2Me)Fe(NO)2][PF6] (3). Electrochemical studies suggest that the redox interconversion among [{Fe(NO)2}9-[·ON2Me]2-] DNIC 3 ↔ [{Fe(NO)2}9-[ON2Me]-] ↔ [{Fe(NO)2}9-[·ON2Me]] DNIC 2 are kinetically feasible, corroborated by the redox shuttle between O-bridged dimerized [(μ-ONMe)2Fe2(NO)4] (4) and [K-18-crown-6-ether)][(ONMe)Fe(NO)2] (5). In parallel with this finding, the electronic structures of [{Fe(NO)2}9-{Fe(NO)2}9-[·ON2Me]2-] DNIC 1, [{Fe(NO)2}9-[·ON2Me]2-] DNIC 2, [{Fe(NO)2}9-[·ON2Me]] DNIC 3, [{Fe(NO)2}9-[ONMe]-]2 DNIC 4, and [{Fe(NO)2}9-[·ONMe]2-] DNIC 5 are evidenced by EPR, SQUID, and Fe K-edge pre-edge analyses, respectively.

Examining the stabilising role of metal centre on inter-ligand delocalisation

Non-innocent ligands are a class of ligands that gains attention in organometallic chemistry in recent years, and many remarkable coordination complexes with multiple non-innocent ligands have been synthesised. These complexes admit special electronic configurations that could be rationalised by “inter-ligand delocalisation”. In this work, we make use of the Principal Interacting Orbital analysis we developed to examine the role of metal centre in these cases. We found that the metal orbitals used in such kind of stabilisation can differ between early and late transition metals, and the geometry of the complex is also influenced by symmetry factors. These analyses not only complement the earlier understanding of “inter-ligand delocalisation”, but also give hint to the controversial roles of transition metal p orbitals in coordination chemistry.

Metal-Tuned Ligand Reactivity Enables CX2 (X = O, S) Homocoupling with Spectator Cu Centers.

Ligand non-innocence is ubiquitous in catalysis with ligands in synthetic complexes contributing as electron reservoirs or co-sites for substrate activation. The latter chemical non-innocence is manifested in H+ storage or relay at sites beyond the metal primary coordination sphere. Reaction of a competent CO2-to-oxalate reduction catalyst, namely, [K(THF)3](Cu3SL), where L3- is a tris(β-diketiminate) cyclophane, with CS2 affords tetrathiooxalate at long reaction times or at high CS2 concentrations, where otherwise an equilibrium is established between the starting species and a complex-CS2 adduct in which the CS2 is bound to the C atom on the ligand backbone. X-ray diffraction analysis of this adduct reveals no apparent metal participation, suggesting an entirely ligand-based reaction controlled by the charge state of the cluster. Thermodynamic parameters for the formation of the aforementioned Cligand-CS2 bond were experimentally determined, and trends with cation Lewis acidity were studied, where more acidic cations shift the equilibrium toward the adduct. Relevance of such an adduct in the reduction of CO2 to oxalate by this complex is supported by DFT studies, similar effects of countercation Lewis acidity on product formation, and the homocoupled heterocumulene product speciation as determined by isotopic labeling studies. Taken together, this system extends chemical non-innocence beyond H+ to effect catalytic transformations involving C-C bond formation and represents the rarest example of metal-ligand cooperativity, that is, spectator metal ion(s) and the ligand as the reaction center.