Chromium-Thiolate Complex Undergoing C-S Bond Cleavage.

The cleavage of C-S bonds represents a crucial step in fossil fuel refinement to remove organosulfur impurities. Efforts are required to identify alternatives that can replace the energy-intensive hydrodesulfurization process currently in use. In this context, we have developed a series of bis-thiolato-ligated CrIII complexes supported by the L2- ligand (L2- = 2,2'-bipyridine-6,6'-diyl(bis(1,1-diphenylethanethiolate), one of them displaying desulfurization of one thiolate of the ligand under reducing and acidic conditions at ambient temperature and atmospheric pressure. While only 5-coordinated complexes were previously isolated by reaction of L2- with 3d metal MIII ions, both 5- and 6-coordinated mononuclear complexes have been obtained in the case of CrIII, viz., [CrIIILCl], [CrIIILCl2]-, and [CrIIILCl(CH3CN)]. The investigation of the reactivity of [CrIIILCl(CH3CN)] under reducing conditions led to a dinuclear [CrIII2L2(µ-Cl)(µ-OH)] compound and, in the presence of protons, to the mononuclear CrIII complex [CrIII(LN2S)2]+, where LN2S- is the partially desulfurized form of L2-. A desulfurization mechanism has been proposed involving the release of H2S, as evidenced experimentally.

Phosphine Oxide Porous Organic Polymers Incorporating Cobalt(II) Ions: Synthesis, Characterization, and Investigation of H2 Production.

Suitably functionalized porous matrices represent versatile platforms to support well-dispersed catalytic centers. In the present study, porous organic polymers (POPs) containing phosphine oxide groups were fabricated to bind transition metals and to be investigated for potential electrocatalytic applications. Cross-linking of mono- and di-phosphine monomers with multiple phenyl substituents was subject to the Friedel-Crafts (F-C) reaction and the oxidation process, which generated phosphine oxide porous polymers with pore capacity up to 0.92 cm3/g and a surface area of about 990 m2/g. The formation of the R3P·BH3 borohydride adduct during synthesis allows to extend the library of phosphine-based monomeric entities when using FeCl3. The porous polymers were loaded with 0.8-4.2 w/w % of cobalt(II) and behaved as hydrogen evolution reaction (HER) catalysts with a Faradaic efficiency of up to 95% (5.81 × 10-5 mol H2 per 11.76 C) and a stable current density during repeated controlled potential experiments (CPE), even though with high overpotentials (0.53-0.68 V to reach a current density of 1 mA·cm-2). These studies open the way to the effectiveness of tailored phosphine oxide POPs produced through an inexpensive and ecofriendly iron-based catalyst and for the insertion of transition metals in a porous architecture, enabling electrochemically driven activation of small molecules.

Bio-inspired, Multifunctional Metal-Thiolate Motif: From Electron Transfer to Sulfur Reactivity and Small-Molecule Activation.

Sulfur-rich metalloproteins and metalloenzymes, containing strongly covalent metal-thiolate (cysteinate) or metal-sulfide bonds in their active site, are ubiquitous in nature. The metal-sulfur motif is a highly versatile tool involved in various biological processes: (i) metal storage, transport, and detoxification; (ii) electron transfer; (iii) activation of the sulfur atom to promote different types of S-based reactions including S-alkylation, S-oxygenation, S-nitrosylation, or disulfide or thiyl radicals formation; (iv) activation of small earth-abundant molecules (such as water, dioxygen, superoxide radical anion, carbon oxides, nitrous oxide, and dinitrogen).This Account describes our investigations carried out during the past 10 years on bio-inspired and biomimetic low-nuclearity complexes containing metal-thiolate bonds. The general objective of these structural, spectroscopic, electrochemical, and catalytic studies was to determine structure-properties-function correlations useful to (i) understanding the peculiar features or the mechanism of the mimicked natural systems and/or (ii) reproducing enzymatic reactivities for specific catalytic applications.By employing a unique highly preorganized N2S2-donor ligand with two thiolate functions, in combination with different first-row transition metals (Mn, Fe, Co, Ni, Cu, Zn, or V), we got access to a series of bio-inspired sulfur-rich complexes displaying a widespread spectrum of structures, properties, and functions. We isolated a dicopper(I) complex that, for the first time, mimicked concomitantly the key structural, spectroscopic, and redox features of the biological CuA center, a highly efficient electron transfer agent involved in the respiratory enzyme cytochrome c oxidase. In the field of sulfur activation, we explored (i) sulfur methylation promoted by a Zn-dithiolate complex that mimics Zn-dependent thiolate alkylation proteins and shows different selectivity compared to the Ni and Co congeners and (ii) a series of Co, Fe, and Mn complexes as the first copper-free systems able to promote thiolate/disulfide interconversion mediated by (de)coordination of halides. Concerning metal-centered reactivity, we investigated two families of metal-thiolate catalysts for small-molecule activation, especially relevant in the fields of sustainable fuel production and energy conversion: (i) two isostructural Mn and Fe dinuclear complexes that activate and reduce dioxygen selectively, either to hydrogen peroxide or water as a function of the experimental conditions; (ii) a family of dinuclear MFe (M = Ni or Fe) hydrogenase mimics active for catalytic H2 evolution both in organic solution and on modified electrodes in water.This Account thus illustrates how the versatility of thiolate ligation can support selected functions for transition metal complexes, depending on the nature of the metal, the nuclearity of the complex, the presence and type of co-ligands, the second coordination sphere effects, and the experimental conditions.

O2 Activation by Non-Heme Thiolate-Based Dinuclear Fe Complexes.

Iron centers featuring thiolates in their metal coordination sphere (as ligands or substrates) are well-known to activate dioxygen. Both heme and non-heme centers that contain iron-thiolate bonds are found in nature. Investigating the ability of iron-thiolate model complexes to activate O2 is expected to improve the understanding of the key factors that direct reactivity to either iron or sulfur. We report here the structural and redox properties of a thiolate-based dinuclear Fe complex, [FeII2(LS)2] (LS2- = 2,2'-(2,2'-bipyridine-6,6'-iyl)bis(1,1-diphenylethanethiolate)), and its reactivity with dioxygen, in comparison with its previously reported protonated counterpart, [FeII2(LS)(LSH)]+. When reaction with O2 occurs in the absence of protons or in the presence of 1 equiv of proton (i.e., from [FeII2(LS)(LSH)]+), unsupported µ-oxo or µ-hydroxo FeIII dinuclear complexes ([FeIII2(LS)2O] and [FeIII2(LS)2(OH)]+, respectively) are generated. [FeIII2(LS)2O], reported previously but isolated here for the first time from O2 activation, is characterized by single crystal X-ray diffraction and Mössbauer, resonance Raman, and NMR spectroscopies. The addition of protons leads to the release of water and the generation of a mixture of two Fe-based "oxygen-free" species. Density functional theory calculations provide insight into the formation of the µ-oxo or µ-hydroxo FeIII dimers, suggesting that a dinuclear µ-peroxo FeIII intermediate is key to reactivity, and the structure of which changes as a function of protonation state. Compared to previously reported Mn-thiolate analogues, the evolution of the peroxo intermediates to the final products is different and involves a comproportionation vs a dismutation process for the Mn and Fe derivate, respectively.

A Non-Heme Diiron Complex for (Electro)catalytic Reduction of Dioxygen: Tuning the Selectivity through Electron Delivery.

In the oxygen reduction reaction (ORR) domain, the investigation of new homogeneous catalysts is a crucial step toward the full comprehension of the key structural and/or electronic factors that control catalytic efficiency and selectivity. Herein, we report a unique non-heme diiron complex that can act as a homogeneous ORR catalyst in acetonitrile solution. This iron(II) thiolate dinuclear complex, [FeII2(LS)(LSH)] ([Fe2SH]+) (LS2- = 2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate)) contains a thiol group in the metal coordination sphere. [Fe2SH]+ is an efficient ORR catalyst both in the presence of a one-electron reducing agent and under electrochemically assisted conditions. However, its selectivity is dependent on the electron delivery pathway; in particular, the process is selective for H2O2 production under chemical conditions (up to ∼95%), whereas H2O is the main product during electrocatalysis (less than ∼10% H2O2). Based on computational work alongside the experimental data, a mechanistic proposal is discussed that rationalizes the selective and tunable reduction of dioxygen.

Hydrogen Evolution from Aqueous Solutions Mediated by a Heterogenized [NiFe]-Hydrogenase Model: Low pH Enables Catalysis through an Enzyme-Relevant Mechanism.

[NiFe]-hydrogenase enzymes are efficient catalysts for H2 evolution but their synthetic models have not been reported to be active under aqueous conditions so far. Here we show that a close model of the [NiFe]-hydrogenase active site can work as a very active and stable heterogeneous H2 evolution catalyst under mildly acidic aqueous conditions. Entry in catalysis is a NiI FeII complex, with electronic structure analogous to the Ni-L state of the enzyme, corroborating the mechanism modification recently proposed for [NiFe]-hydrogenases.

Solvent- and Halide-Induced (Inter)conversion between Iron(II)-Disulfide and Iron(III)-Thiolate Complexes.

Disulfide/thiolate interconversion controlled by Cu is proposed to be involved in relevant biological processes. In analogy to Cu, it can be envisaged that Fe also participates in the control of similar biological processes. We describe here Fe complexes that undergo FeIII -thiolate/FeII -disulfide (inter)conversion mediated by halide (de)coordination, and by the nature of the solvent. The dinuclear FeII -disulfide complex [FeII2 (LSSL)]2+ ((LS)2- =2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate), (LSSL)2- =the corresponding disulfide ligand) shows solvent-dependent properties. Whereas in a non-coordinating solvent (CH2 Cl2 ) the dinuclear FeII -disulfide complex is the only stable form, in the presence of coordinating solvents like MeCN or DMF it is partly or fully converted into mononuclear FeIII -thiolate species having a bound solvent molecule ([FeIII (LS)(Solv)]+ , Solv=DMF, MeCN). Addition of Cl- to a CH2 Cl2 solution containing the FeII -disulfide dinuclear complex leads to the fast and quantitative formation of a mononuclear FeIII -thiolate species with a bound Cl- , that is, ([FeIII (LS)Cl]). The reverse reaction can be achieved by addition of Li[[B(C6 F5 )4 ]. In relation to the metal-sulfur electronic distribution, the comparison between the redox properties of the Fe, Mn and Co complexes involved in these MIII -thiolate/MII -disulfide interconversion processes allow one to rationalize their respective efficiency.

Experimental and Theoretical Identification of the Origin of Magnetic Anisotropy in Intermediate Spin Iron(III) Complexes.

The complexes [FeLN2S2 X] [in which LN2S2 =2,2'-(2,2'-bipryridine-6,6'-diyl)bis(1,1'-diphenylethanethiolate) and X=Cl, Br and I], characterized crystallographically earlier and here (Fe(L)Br), reveal a square pyramidal coordinated FeIII ion. Unusually, all three complexes have intermediate spin ground states. Susceptibility measurements, powder cw X- and Q-band EPR spectra, and zero-field powder Mössbauer spectra show that all complexes display distinct magnetic anisotropy, which has been rationalized by DFT calculations.

Heterogenization of a [NiFe] Hydrogenase Mimic through Simple and Efficient Encapsulation into a Mesoporous MOF.

In the quest for new, efficient, and noble-metal-free H2-evolution catalysts, hydrogenase enzymes are a source of inspiration. Here, we describe the development of a new hybrid material based on a structural and functional [NiFe]-hydrogenase model complex (NiFe) incorporated into the Zr-based MOF PCN-777. The bulk NiFe@PCN-777 material was synthesized by simple encapsulation. Characterization by solid-state NMR and IR spectroscopy, SEM-EDX, ICP-OES, and gas adsorption confirmed the inclusion of the guest. FTO-supported thin films of the NiFe@PCN-777 composite were obtained by electrophoretic deposition of the bulk material and characterized by SEM-EDX, ICP-OES, and cyclic voltammetry. The average surface concentration of electroactive NiFe catalyst in the film was found to be ∼9.6 × 10-10 mol cm-2, implying that a surprisingly high fraction (37%) of NiFe units incorporated in the MOF are electroactive. By cyclic voltammetry, we showed that NiFe maintains its electrocatalytic capabilities for H+ reduction inside the MOF cavities, even if under controlled-potential electrolysis conditions the activity of NiFe cannot be discerned from that of free PCN-777 and FTO.

Molecular Catalysts for N2 Reduction: State of the Art, Mechanism, and Challenges.

Fixation of atmospheric nitrogen is central for the production of ammonia, which is the source of nitrogen fertilizers and is also emerging as a promising renewable fuel. While the development of efficient molecular-based artificial nitrogen fixation systems working under mild conditions is probably a Holy Grail, the catalytic reduction of N2 by transition-metal complexes is-above all-the main instrument to progress in the mechanistic understanding of N2 splitting. In this Minireview we first give an overview of molecular-based catalytic systems, including recent breakthroughs, and then we illustrate the alternative pathways for N2 reduction. We mainly focus on multistep hydrogenation of N2 by separated proton and electron sources, with a particular attention for the possibility of proton-coupled electron transfer events. Finally, we try to identify the key factors to achieve catalytic reduction of dinitrogen by metal complexes and to enhance their efficiency.

A High-Valent Non-Heme µ-Oxo Manganese(IV) Dimer Generated from a Thiolate-Bound Manganese(II) Complex and Dioxygen.

This study deals with the unprecedented reactivity of dinuclear non-heme MnII -thiolate complexes with O2 , which dependent on the protonation state of the initial MnII dimer selectively generates either a di-µ-oxo or µ-oxo-µ-hydroxo MnIV complex. Both dimers have been characterized by different techniques including single-crystal X-ray diffraction and mass spectrometry. Oxygenation reactions carried out with labeled 18 O2 unambiguously show that the oxygen atoms present in the MnIV dimers originate from O2 . Based on experimental observations and DFT calculations, evidence is provided that these MnIV species comproportionate with a MnII precursor to yield µ-oxo and/or µ-hydroxo MnIII dimers. Our work highlights the delicate balance of reaction conditions to control the synthesis of non-heme high-valent µ-oxo and µ-hydroxo Mn species from MnII precursors and O2 .

Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase.

Hydrogen production through water splitting is one of the most promising solutions for the storage of renewable energy. [NiFe] hydrogenases are organometallic enzymes containing nickel and iron centres that catalyse hydrogen evolution with performances that rival those of platinum. These enzymes provide inspiration for the design of new molecular catalysts that do not require precious metals. However, all heterodinuclear NiFe models reported so far do not reproduce the Ni-centred reactivity found at the active site of [NiFe] hydrogenases. Here, we report a structural and functional NiFe mimic that displays reactivity at the Ni site. This is shown by the detection of two catalytic intermediates that reproduce structural and electronic features of the Ni-L and Ni-R states of the enzyme during catalytic turnover. Under electrocatalytic conditions, this mimic displays high rates for H2 evolution (second-order rate constant of 2.5 × 104 M-1 s-1; turnover frequency of 250 s-1 at 10 mM H+ concentration) from mildly acidic solutions.

Multifrequency cw-EPR and DFT Studies of an Apparent Compressed Octahedral Cu(II) Complex.

The syntheses and single-crystal X-ray structures of the mononuclear complexes [Cu(bmet)](ClO4)2·H2O, [Cu(bmet)]Br2·2MeCN, and [Zn(bmet)](ClO4)2·H2O (bmet = N,N'-bis(2,2'-bipyridin-6-ylmethyl)ethane-1,2-diamine) are described. All three complexes feature a central metal ion bound to all six N atoms of the bmet ligand, which displays a meridional-facial-facial-meridional (mffm) configuration. The three complexes show one N-M-N axis to be significantly shorter than the others in agreement with an apparent compressed octahedral geometry. The X-ray structures of a single crystal of [Cu(bmet)](ClO4)2·0.375H2O resolved from data recorded at different temperatures display no remarkable structural modifications. However, they all display both as a powder and, in solution, an axial g1 > g2 ≳ g3 > g(e) electron paramagnetic resonance (EPR) pattern at low temperature, which is indicative of tetragonally elongated octahedra, while at room temperature the Q-band EPR spectra display a more rhombic g1 ≳ g2 > g3 > g(e) pattern. The fully density functional theory optimized structure of the Cu(II) complexes displays significant structural modifications only along one N(imine)-M-N(amine) axis resulting in an elongated octahedral structure. Furthermore, the EPR parameters predicted from this structure are comparable to those determined experimentally from the axial EPR signal recorded at low temperature, consistent with the unpaired electron residing mainly in the {3d(x(2)-y(2))} orbital. The structural and electronic properties of [Cu(bmet)](2+) are different from those in other previously described dynamic Jahn-Teller systems. We propose that these data can be rationalized by a dynamic Jahn-Teller effect perturbed by the strain of the hexadentate bmet ligand.

An Experimental and Theoretical Investigation on Pentacoordinated Cobalt(III) Complexes with an Intermediate S=1 Spin State: How Halide Ligands Affect their Magnetic Anisotropy.

Understanding the factors that control the magnitude and symmetry of magnetic anisotropy should facilitate the rational design of mononuclear metal complexes in the quest for single-molecule magnets (SMMs), based on a single metal ion, with high blocking temperatures and large energy barriers. The best strategy is to define magnetostructural correlations through the investigation of a series of metal complexes. It has been demonstrated that the main contribution to the magnetic anisotropy arises from the spin-orbit coupling (SOC) effect in metal-ion-based systems, so current studies focus particularly on the use of both ligands and metal ions possessing a large SOC. In this context, we report a unique series of halide Co(III) complexes, [CoL(X)], with X=Cl, Br, I (CoX) and L=2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate), which possess a rare intermediate S=1 spin ground state. The S=1 Co(III) complexes are attractive species because they possess a remarkably large axial zero-field splitting (defined by D from the following Hamiltonian: H=DSz (2) ), as well as the halide ligands inducing large SOC constants. The single-crystal X-ray structures reveal that the CoBr and CoI complexes are isostructural with the previously described CoCl complex. Their coordination sphere displays a distorted pentacoordinated square pyramidal geometry, with the halide located in the Co(III) axial position. Large positive D values of 35, 26, and 18 cm(-1) are found for CoCl, CoBr, and CoI, respectively, through analysis of the magnetic susceptibility data as a function of temperature. To rationalize this trend, theoretical calculations based on both density functional theory (DFT) and complete active space self-consistent field (CASSCF) methods are performed successfully. Both the sign and magnitude of D are predicted remarkably well by these theoretical approaches. The DFT calculations also show that the resulting D values originate from a balance of several contributions, and that many factors, including differences in their structural properties and in the contribution of the halide, should be taken into account to explain the trend of D in this series of complexes.

Effect of the Metal on Disulfide/Thiolate Interconversion: Manganese versus Cobalt.

It has recently been proposed that disulfide/thiolate interconversion supported by transition-metal ions is involved in several relevant biological processes. In this context, the present contribution represents a unique investigation of the effect of the coordinated metal (M) on the M(n+)-disulfide/M((n+1)+)-thiolate switch properties. Like its isostructural Co(II)-based parent compound, Co(II)2SS (Angew. Chem. Int. Ed.- 2014, 53, 5318), the new dinuclear disulfide-bridged Mn(II) complex Mn(II)2SS can undergo an M(II)-disulfide/M(III)-thiolate interconversion, which leads to the first disulfide/thiolate switch based on Mn. The coordination of iodide to the metal ion stabilizes the oxidized form, as the disulfide is reduced to the thiolate. The reverse process, which involves the reduction of M(III) to M(II) with the concomitant oxidation of the thiolates, requires the release of iodide. The Mn(II)2SS complex slowly reacts with Bu4NI in CH2Cl2 to afford the mononuclear Mn(III)-thiolate complex Mn(III)I. The process is much slower (ca. 16 h) and much less efficient (ca. 30% yield) with respect to the instantaneous and quantitative conversion of Co(II)2SS into Co(III)I under similar conditions. This distinctive behavior can be rationalized by considering the different electrochemical properties of the involved Co and Mn complexes and the DFT-calculated driving force of the disulfide/thiolate conversion. For both Mn and Co systems, M(II)-disulfide/M(III)-thiolate interconversion is reversible. However, when the iodide is removed with Ag(+), the M(II)2SS complexes are regenerated, albeit much slower for Mn than for Co systems.

How Accurately Can Extended X-ray Absorption Spectra Be Predicted from First Principles? Implications for Modeling the Oxygen-Evolving Complex in Photosystem II.

First principle calculations of extended X-ray absorption fine structure (EXAFS) data have seen widespread use in bioinorganic chemistry, perhaps most notably for modeling the Mn4Ca site in the oxygen evolving complex (OEC) of photosystem II (PSII). The logic implied by the calculations rests on the assumption that it is possible to a priori predict an accurate EXAFS spectrum provided that the underlying geometric structure is correct. The present study investigates the extent to which this is possible using state of the art EXAFS theory. The FEFF program is used to evaluate the ability of a multiple scattering-based approach to directly calculate the EXAFS spectrum of crystallographically defined model complexes. The results of these parameter free predictions are compared with the more traditional approach of fitting FEFF calculated spectra to experimental data. A series of seven crystallographically characterized Mn monomers and dimers is used as a test set. The largest deviations between the FEFF calculated EXAFS spectra and the experimental EXAFS spectra arise from the amplitudes. The amplitude errors result from a combination of errors in calculated S0(2) and Debye-Waller values as well as uncertainties in background subtraction. Additional errors may be attributed to structural parameters, particularly in cases where reliable high-resolution crystal structures are not available. Based on these investigations, the strengths and weaknesses of using first-principle EXAFS calculations as a predictive tool are discussed. We demonstrate that a range of DFT optimized structures of the OEC may all be considered consistent with experimental EXAFS data and that caution must be exercised when using EXAFS data to obtain topological arrangements of complex clusters.

Calcium and heterometallic manganese-calcium complexes supported by tripodal pyridine-carboxylate ligands: structural, EPR and theoretical investigations.

Carboxylate-bridged Mn(II)-Ca(II) complexes are potentially relevant for mimicking the first stages of the Oxygen-Evolving Complex (OEC) assembly process. Here, we report on new homonuclear Ca(II) and heteronuclear Mn(II)­Ca(II) complexes with carboxylate-functionalized tripodal tris(2-pyridylmethyl)amine ligands, the heptadentate H3tpaa, previously reported, and the new hexadentate H2tpada, containing respectively three and two carboxylate units. The mononuclear [Ca(Htpaa)(OH2)] (Ca1) and dinuclear [Ca(tpada)(OH2)2]2 (Ca2) calcium complexes, as well as the tetranuclear [{Mn(tpaa)}2{Ca(OH2)5(µ-OH2)}2][Mn(tpaa)]2 (Mn2Ca2·2Mn) and dinuclear [Mn(tpada)ClCa(OH2)2.67(MeOH)2.33]Cl (MnCa) heterometallic species have been structurally characterized; the syntheses of Ca1 and Mn2Ca2·2Mn being previously reported by us (Inorg. Chem., 2015, 54, 1283). The Mn(II) and Ca(II) are linked by two µ1,1-bridging carboxylates in MnCa, while only one µ1,3-carboxylate bridge connects each Ca2+ ion to each Mn(II) in Mn2Ca2. A variable number of water molecules (n = 1 to 7) are coordinated to Ca in all complexes, most of them being involved in hydrogen-bond networks, in analogy to what occurs in the photosystem II. All donor atoms of the tpaa3- and tpada2- ligands are coordinated to the Mn2+ ions, despite the unusually long distance between the Mn2+ ion and the tertiary amine imposed by the constraining nature of the ligands, as supported by theoretical calculations. Solid state EPR spectroscopy, in combination with DFT calculations, has also shown that the Ca2+ ion has an effect on the electronic parameters (zero field splitting) of the linked Mn(II) in the case of MnCa (µ1,1-carboxylate bridges). In Mn2Ca2 (µ1,3-carboxylate bridge) the Ca2+ ion induces only slight structural changes in the Mn coordination sphere.

Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol.

Herein, we describe an uncommon example of a manganese-thiolate complex, which is capable of activating dioxygen and catalyzing its two-electron reduction to generate H2O2. The structurally characterized dimercapto-bridged Mn(II) dimer [Mn(II)2(LS)(LSH)]ClO4 (Mn(II)2SH) is formed by reaction of the LS ligand (2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate)) with Mn(II). The unusual presence of a pendant thiol group bound to one Mn(II) ion in Mn(II)2SH is evidenced both in the solid state and in solution. The Mn(II)2SH complex reacts with dioxygen in CH3CN, leading to the formation of a rare mono-µ-hydroxo dinuclear Mn(III) complex, [(Mn(III)2(LS)2(OH)]ClO4 (Mn(III)2OH), which has also been structurally characterized. When Mn(II)2SH reacts with O2 in the presence of a proton source, 2,6-lutidinium tetrafluoroborate (up to 50 equiv), the formation of a new Mn species is observed, assigned to a bis-µ-thiolato dinuclear Mn(III) complex with two terminal thiolate groups (Mn(III)2), with the concomitant production of H2O2 up to ∼40% vs Mn(II)2SH. The addition of a catalytic amount of Mn(II)2SH to an air-saturated solution of MenFc (n = 8 or 10) and 2,6-lutidinium tetrafluoroborate results in the quantitative and efficient oxidation of MenFc by O2 to afford the respective ferrocenium derivatives (MenFc(+), with n = 8 or 10). Hydrogen peroxide is mainly produced during the catalytic reduction of dioxygen with 80-84% selectivity, making the Mn(II)2SH complex a rare Mn-based active catalyst for two-electron O2 reduction.

Ca K-edge XAS as a probe of calcium centers in complex systems.

Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.

On the road to MM'X polymers: redox properties of heterometallic Ni···Pt paddlewheel complexes.

On the quest of heterometallic mixed-valence MM'X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(µ-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(µ-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(µ-OSCPh)4Pt} core. Experimental and theoretical analyses indicate that a NiPt-Cl/Cl-NiPt isomerization process occurs in the oxidized species. The electronic structure of the reduced system shows two unpaired electrons, one located in a d(x(2)-y(2)) orbital of the Ni(II) ion and a second in the antibonding d(z(2)-dz(2)) combination from the Ni(II) and Pt(II) centers. Oxidation occurs by removing one electron from this second multicenter molecular orbital. Although the mixed-valence character of the oxidized species makes the isolation of MM'X chains very attractive, such polymeric structure is prevented by the low Pt-Cl···Ni interaction energy and the high tendency of Ni centers to coordinate water molecules. Thus, this work offers valuable insights and hints to engage the production of heterometallic mixed-valence MM'X chains, which still is a challenging task.