Identification, Characterization, and Electronic Structures of Interconvertible Cobalt-Oxygen TAML Intermediates.

The reaction of Li[(TAML)CoIII]·3H2O (TAML = tetraamido macrocyclic tetraanionic ligand) with iodosylbenzene at 253 K in acetone in the presence of redox-innocent metal ions (Sc(OTf)3 and Y(OTf)3) or triflic acid affords a blue species 1, which is converted reversibly to a green species 2 upon cooling to 193 K. The electronic structures of 1 and 2 have been determined by combining advanced spectroscopic techniques (X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), X-ray absorption spectroscopy/extended X-ray absorption fine structure (XAS/EXAFS), and magnetic circular dichroism (MCD)) with ab initio theoretical studies. Complex 1 is best represented as an S = 1/2 [(Sol)(TAML•+)CoIII---OH(LA)]- species (LA = Lewis/Brønsted acid and Sol = solvent), where an S = 1 Co(III) center is antiferromagnetically coupled to S = 1/2 TAML•+, which represents a one-electron oxidized TAML ligand. In contrast, complex 2, also with an S = 1/2 ground state, is found to be multiconfigurational with contributions of both the resonance forms [(H-TAML)CoIV═O(LA)]- and [(H-TAML•+)CoIII═O(LA)]-; H-TAML and H-TAML•+ represent the protonated forms of TAML and TAML•+ ligands, respectively. Thus, the interconversion of 1 and 2 is associated with a LA-associated tautomerization event, whereby H+ shifts from the terminal -OH group to TAML•+ with the concomitant formation of a terminal cobalt-oxo species possessing both singlet (SCo = 0) Co(III) and doublet (SCo = 1/2) Co(IV) characters. The reactivities of 1 and 2 at different temperatures have been investigated in oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions to compare the activation enthalpies and entropies of 1 and 2.

Two Allogons of an O2 -activating Bis(disiloxido)ferrate(II) Accessible Selectively just by Variation of the Crystallization Temperature.

Deprotonation of O(iPr2 SiOH)2 (iPr LH2 ) with LiOtBu followed by reaction with FeCl2 in THF led to the complex [iPr L2 Fe][Li(THF)2 ]2 , 2, which represents a structural and spectroscopic model of the α-Fe sites of Fe/ZSM-5. Reaction with O2 in THF solution proceeds rather fast and is complete within 200 ms; an intermediate O2 adduct could not be identified by stopped-flow methods. Cooling blue solutions of 2 to -80 °C led to the growth of blue crystals of 2⋅THF, the analysis of which by XRD revealed a FeO4 core that is somewhat distorted from planarity towards a tetrahedral structure. By contrast, cooling such solutions to -30 °C led to pink crystals of an allogon featuring a perfectly square planar FeO4 entity. Hence, 2 represents a unique case where two different structural isomers (allogons) can be crystallized from the same solvent selectively, controlled by the temperature. DFT calculations were performed to understand this finding.

Valence-to-core X-ray emission spectroscopy of transition metal tetrahalides: mechanisms governing intensities.

Valence-to-core (VtC) X-ray emission spectroscopy offers the opportunity to probe the valence electronic structure of a system filtered by selection rules. From this, the nature of its ligands can be inferred. While a preceding 1s ionization creates a core hole, in VtC XES this core hole is filled with electrons from mainly ligand based orbitals. In this work, we investigated the trends in the observed VtC intensities for a series of transition metal halides, which spans the first row transition metals from manganese to copper. Further, with the aid of computational studies, we corroborated these trends and identified the mechanisms and factors that dictate the observed intensity trends. Small amounts of metal p contribution to the ligand orbitals are known to give rise to intensity of a VtC transition. By employing an LCAO (linear combination of atomic orbitals) approach, we were able to assess the amount of metal p contribution to the ligand molecular orbitals, as well as the role of the transition dipole moment and correlate these factors to the experimentally observed intensities. Finally, by employing an ano (atomic natural orbital) basis set within the calculations, the nature of the metal p contribution (3p vs. 4p) was qualitatively assessed and their trends discussed within the same transition metal halide series.

Oxygen sensitivity of [FeFe]-hydrogenase: a comparative study of active site mimics inside vs. outside the enzyme.

[FeFe]-hydrogenase is nature's most efficient proton reducing and H2-oxidizing enzyme. However, biotechnological applications are hampered by the O2 sensitivity of this metalloenzyme, and the mechanism of aerobic deactivation is not well understood. Here, we explore the oxygen sensitivity of four mimics of the organometallic active site cofactor of [FeFe]-hydrogenase, [Fe2(adt)(CO)6-x(CN)x]x- and [Fe2(pdt)(CO)6-x(CN)x]x- (x = 1, 2) as well as the corresponding cofactor variants of the enzyme by means of infrared, Mössbauer, and NMR spectroscopy. Additionally, we describe a straightforward synthetic recipe for the active site precursor complex Fe2(adt)(CO)6. Our data indicate that the aminodithiolate (adt) complex, which is the synthetic precursor of the natural active site cofactor, is most oxygen sensitive. This observation highlights the significance of proton transfer in aerobic deactivation, and supported by DFT calculations facilitates an identification of the responsible reactive oxygen species (ROS). Moreover, we show that the ligand environment of the iron ions critically influences the reactivity with O2 and ROS like superoxide and H2O2 as the oxygen sensitivity increases with the exchange of ligands from CO to CN-. The trends in aerobic deactivation observed for the model complexes are in line with the respective enzyme variants. Based on experimental and computational data, a model for the initial reaction of [FeFe]-hydrogenase with O2 is developed. Our study underscores the relevance of model systems in understanding biocatalysis and validates their potential as important tools for elucidating the chemistry of oxygen-induced deactivation of [FeFe]-hydrogenase.

A configuration-based heatbath-CI for spin-adapted multireference electronic structure calculations with large active spaces.

This work reports on a spin-pure configuration-based implementation of the heatbath configuration interaction (HCI) algorithm for selective configuration interaction. Besides the obvious advantage of being spin-pure, the presented method combines the compactness of the configurational ansatz with the known efficiency of the HCI algorithm and a variety of algorithmic and conceptual ideas to achieve a high level of performance. In particular, through pruning of the selected configurational space after HCI selection by means of a more strict criterion, a more compact wavefunction representation is obtained. Moreover, the underlying logic of the method allows us to minimize the number of redundant matrix-matrix multiplications while making use of just-in-time compilation to achieve fast diagonalization of the Hamiltonian. The critical search for 2-electron connections within the configurational space is facilitated by a tree-based representation thereof as suggested previously by Gopal et al. Usage of a prefix-based parallelization and batching during the calculation of the PT2-correction leads to a good load balancing and significantly reduced memory requirements for these critical steps of the calculation. In this way, the need for a semistochastic approach to the PT2 correction is avoided even for large configurational spaces. Finally, several test-cases are discussed to demonstrate the strengths and weaknesses of the presented method.

Electrochemistry and Reactivity of Chelation-stabilized Hypervalent Bromine(III) Compounds.

Hypervalent bromine(III) reagents possess a higher electrophilicity and a stronger oxidizing power compared to their iodine(III) counterparts. Despite the superior reactivity, bromine(III) reagents have a reputation of hard-to-control and difficult-to-synthesize compounds. This is partly due to their low stability, and partly because their synthesis typically relies on the use of the toxic and highly reactive BrF3 as a precursor. Recently, we proposed chelation-stabilized hypervalent bromine(III) compounds as a possible solution to both problems. First, they can be conveniently prepared by electro-oxidation of the corresponding bromoarenes. Second, the chelation endows bromine(III) species with increased stability while retaining sufficient reactivity, comparable to that of iodine(III) counterparts. Finally, their intrinsic reactivity can be unlocked in the presence of acids. Herein, an in-depth mechanistic study of both the electrochemical generation and the reactivity of the bromine(III) compounds is disclosed, with implications for known applications and future developments in the field.

A Copper Cage-Complex as Mimic of the pMMO CuC Site.

The active site of particulate methane monooxygenase (pMMO) and its mechanism of action are not known. Recently, the CuC site emerged as a potential active site, but to date it lacks any study on biomimetic resemblance of the coordination environment provided by the enzyme. Here, the synthesis of a cage ligand providing such an environment is reported. Copper is incorporated, and coordination occurs by the two imidazole and one carboxylate group offered by the ligand. Depending on the oxidation state, it can adopt different coordination modes, as evidenced by the solid-state structures and computational investigation. The copper(I) state readily reacts with dioxygen and thereby undergoes CH activation. Moreover, the catalytic aerobic oxidation of hydroquinones as ubiquinol mimics is shown. Clean one-electron oxidation occurs under mild conditions and EPR analysis of the copper(II) state in the presence of water reveals striking similarities to the data obtained from pMMO.

Modern multireference methods and their application in transition metal chemistry.

Transition metal chemistry is a challenging playground for quantum chemical methods owing to the simultaneous presence of static and dynamic electron correlation effects in many systems. Wavefunction based multireference (MR) methods constitute a physically sound and systematically improvable Ansatz to deal with this complexity but suffer from some conceptual difficulties and high computational costs. The latter problem partially arises from the unfavorable scaling of the Full Configuration Interaction (Full-CI) problem which in the majority of MR methods is solved for a subset of the molecular orbital space, the so-called active space. In the last years multiple methods such as modern variants of selected CI, Full-CI Quantum Monte Carlo (FCIQMC) and the density matrix renormalization group (DMRG) have been developed that solve the Full-CI problem approximately for a fraction of the computational cost required by conventional techniques thereby significantly extending the range of applicability of modern MR methods. This perspective review outlines recent advancements in the field of MR electronic structure methods together with the resulting chances and challenges for theoretical studies in the field of transition metal chemistry. In light of its emerging importance a special focus is put on the selection of adequate active spaces and the concomitant development of numerous selection aides in recent years.

Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids.

Recent experiments have shown that the organic free radical 1,3-bisdiphenylene-2-phenylallyl (BDPA) can induce an Overhauser effect dynamic nuclear polarization in insulating solids, a feat previously considered not to be possible. Here, we establish that this peculiar ability of the BDPA radical stems from its mixed-valence nature and the ensuing intramolecular charge transfer. Using state-of-the-art DMRGSCF calculations, we confirm the class II mixed-valence nature of BDPA with the characteristic double-well potential energy surface, and we investigate the mechanism of the consequent electron hopping. A two-component vibronic Hamiltonian is then employed to compute the rate of electron hopping from a quantum dynamical time-propagation of the density matrix. The predicted hyperfine coupling oscillations indeed fall within the frequency range required for an Overhauser effect. The paradigm of mixed-valence compounds as a mining source opens many possibilities for the development and fine tuning of novel polarizing agents.

Electrochemically Catalyzed Newman-Kwart Rearrangement: Mechanism, Structure-Reactivity Relationship, and Parallels to Photoredox Catalysis.

The facilitation of redox-neutral reactions by electrochemical injection of holes and electrons, also known as "electrochemical catalysis", is a little explored approach that has the potential to expand the scope of electrosynthesis immensely. To systematically improve existing protocols and to pave the way toward new developments, a better understanding of the underlying principles is crucial. In this context, we have studied the Newman-Kwart rearrangement of O-arylthiocarbamates to the corresponding S-aryl derivatives, the key step in the synthesis of thiophenols from the corresponding phenols. This transformation is a particularly useful example because the conventional method requires temperatures up to 300 °C, whereas electrochemical catalysis facilitates the reaction at room temperature. A combined experimental-quantum chemical approach revealed several reaction channels and rendered an explanation for the relationship between the structure and reactivity. Furthermore, it is shown how rapid cyclic voltammetry measurements can serve as a tool to predict the feasibility for specific substrates. The study also revealed distinct parallels to photoredox-catalyzed reactions, in which back-electron transfer and chain propagation are competing pathways.

Modulating Effect of Ligand Charge on the Electronic Properties of 2Ni-2S Structures and Implications for Biological 2M-2S Sites.

Sulfur-bridged bimetallic 2M-2S type structures are essential cofactors that participate in biological long-range electron transport and metabolism. Metal-sulfur bond covalency is a decisive property for inner sphere (through-bond) type electron transfer that dominates in buried or hydrophobic protein environments. This work reports on a combined experimental and computational study of the effect of ligand charge on the electronic structure of a 2Ni-2S model site that adopts the biologically relevant S = 1/2 redox state. Starting out from an isostructural dinickel(1.5+)-dithiophenolate platform with sulfur-bridged tetrahedral Ni sites, η2:η2-µ-coordination of the S = 1/2 [2Ni-2S]+ core to either a neutral π-system or strongly σ-donating cyclohexadienido renders its electronic structure substantially different. Density functional theory analysis corroborates pulse and continuous wave electron paramagnetic resonance data that associate co-ligand charge with the significant change in the mechanism and size of electron-31P nuclear spin hyperfine coupling to a phosphine reporter ligand at each nickel center. An increasing level of charge donation attenuates direct and through-bridge electronic coupling of the metal sites, resulting in a stronger electronic coupling of the 2Ni-2S core to its terminal phosphine donors. Drawing a connection to biological 2M-2S sites, our 2Ni-2S system indicates that a fine balance of intracore and core-protein electronic coupling is key to biological function for which the degree of charge donation by peripheral donors appears to be a significant parameter.

Homogeneously Catalyzed Electroreduction of Carbon Dioxide-Methods, Mechanisms, and Catalysts.

The utilization of CO2 via electrochemical reduction constitutes a promising approach toward production of value-added chemicals or fuels using intermittent renewable energy sources. For this purpose, molecular electrocatalysts are frequently studied and the recent progress both in tuning of the catalytic properties and in mechanistic understanding is truly remarkable. While in earlier years research efforts were focused on complexes with rare metal centers such as Re, Ru, and Pd, the focus has recently shifted toward earth-abundant transition metals such as Mn, Fe, Co, and Ni. By application of appropriate ligands, these metals have been rendered more than competitive for CO2 reduction compared to the heavier homologues. In addition, the important roles of the second and outer coordination spheres in the catalytic processes have become apparent, and metal-ligand cooperativity has recently become a well-established tool for further tuning of the catalytic behavior. Surprising advances have also been made with very simple organocatalysts, although the mechanisms behind their reactivity are not yet entirely understood. Herein, the developments of the last three decades in electrocatalytic CO2 reduction with homogeneous catalysts are reviewed. A discussion of the underlying mechanistic principles is included along with a treatment of the experimental and computational techniques for mechanistic studies and catalyst benchmarking. Important catalyst families are discussed in detail with regard to mechanistic aspects, and recent advances in the field are highlighted.

An ab initio multireference study of reductive eliminations from organoferrates(iii) in the gas-phase: it is all about the spin state.

Organoferrates(iii) of the composition [FeR3R']- have previously been identified in multiple studies as reaction intermediates during Fe-mediated cross coupling reactions. They are readily formed under reaction conditions and are able to efficiently eliminate cross coupling products which is a key step of the total reaction. However, only little is known about the electronic and structural properties of these organoferrates(iii) and the mechanistic details of the reductive elimination. In this work modern ab initio electronic structure methods on the basis of the density matrix renormalization group (DMRG) are used to study the properties and reactivity of a set of eight organoferrates(iii) with composition [Ph3FeR]- that have been investigated previously by mass-spectrometry experiments. The presented results provide a detailed picture about the reaction mechanism that explains the experimentally observed chemoselectivity in the gas-phase for the majority of cases. An interesting aspect of the proposed mechanism is the central role of the total spin which changes in the course of the reaction and governs the type of reaction mechanism. Eventually the applied computational procedures are thoroughly discussed in view of the conceptual and technical difficulties that were faced during the conducted studies.

An Ab Initio Computational Study of Electronic and Structural Factors in the Isomerization of Donor-Acceptor Stenhouse Adducts.

In this work, the photochemically and thermally induced isomerization of multiple donor-acceptor Stenhouse adducts (DASAs) of the first, second, and third generation is studied by means of state-of-the-art ab initio electronic structure methods leading to new insight into multiple facets of the reaction mechanism. Importantly, prior to any studies of the reaction mechanism, a set of test calculations demonstrate the suitability of the applied ADC(2) and CC2 methods in the present context. An important aspect in this regard is the availability of electronic energies and gradients under implicit consideration of solvent effects. On the basis of calculated reaction energies and barriers as well as a thorough analysis of the wave function compositions, interesting features of the reaction mechanism are deduced. For example, the closed form of second- and third-generation DASAs can be significantly stabilized by π - π interactions between the donor and acceptor termini when certain structural requirements are fulfilled. The central point of this work concerns the delicate balance between neutral and zwitterionic resonance structures that governs the relative barrier height for the crucial C2-C3 and C3-C4 bond rotations. Finally, a set of calculations on yet unreported derivatives highlights how this balance and hence the barrier heights can be tuned through variation of the donor-acceptor strength as well as the solvent polarity.

Synthesis of Benzoxazoles Using Electrochemically Generated Hypervalent Iodine.

The indirect ("ex-cell") electrochemical synthesis of benzoxazoles from imines using a redox mediator based on the iodine(I)/iodine(III) redox couple is reported. Tethering the redox-active iodophenyl subunit to a tetra-alkylammonium moiety allowed for anodic oxidation to be performed without supporting electrolyte. The mediator salt can be easily recovered and reused. Our "ex-cell" approach toward the electrosynthesis of benzoxazoles is compatible with a range of redox-sensitive functional groups. An unprecedented concerted reductive elimination mechanism for benzoxazole formation is proposed on the basis of control experiments and DFT calculations.

EPR/ENDOR and Theoretical Study of the Jahn-Teller-Active [HIPTN3N]MoVL Complexes (L = N-, NH).

The molybdenum trisamidoamine (TAA) complex [Mo] {[3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2N]Mo} carries out catalytic reduction of N2 to ammonia (NH3) by protons and electrons at room temperature. A key intermediate in the proposed [Mo] nitrogen reduction cycle is nitridomolybdenum(VI), [Mo(VI)]N. The addition of [e-/H+] to [Mo(VI)]N to generate [Mo(V)]NH might, in principle, follow one of three possible pathways: direct proton-coupled electron transfer; H+ first and then e-; e- and then H+. In this study, the paramagnetic Mo(V) intermediate {[Mo]N}- and the [Mo]NH transfer product were generated by irradiating the diamagnetic [Mo]N and {[Mo]NH}+ Mo(VI) complexes, respectively, with γ-rays at 77 K, and their electronic and geometric structures were characterized by electron paramagnetic resonance and electron nuclear double resonance spectroscopies, combined with quantum-chemical computations. In combination with previous X-ray studies, this creates the rare situation in which each one of the four possible states of [e-/H+] delivery has been characterized. Because of the degeneracy of the electronic ground states of both {[Mo(V)]N}- and [Mo(V)]NH, only multireference-based methods such as the complete active-space self-consistent field (CASSCF) and related methods provide a qualitatively correct description of the electronic ground state and vibronic coupling. The molecular g values of {[Mo]N}- and [Mo]NH exhibit large deviations from the free-electron value ge. Their actual values reflect the relative strengths of vibronic and spin-orbit coupling. In the course of the computational treatment, the utility and limitations of a formal two-state model that describes this competition between couplings are illustrated, and the implications of our results for the chemical reactivity of these states are discussed.

A projected approximation to strongly contracted N-electron valence perturbation theory for DMRG wavefunctions.

A novel approach to strongly contracted N-electron valence perturbation theory (SC-NEVPT2) as a means of describing dynamic electron correlation for quantum chemical density matrix renormalization group (DMRG) calculations is presented. In this approach the strongly contracted perturber functions are projected onto a renormalized Hilbert space. Compared to a straightforward implementation of SC-NEVPT2 with DMRG wavefunctions, the computational scaling and storage requirements are reduced. This favorable scaling opens up the possibility of calculations with larger active spaces. A specially designed renormalization scheme ensures that both the electronic ground state and the perturber functions are well represented in the renormalized Hilbert space. Test calculations on the N2 and [Cu2O2(en)2](2+) demonstrate some key properties of the method and indicate its capabilities.

Spin orbit coupling for molecular ab initio density matrix renormalization group calculations: Application to g-tensors.

Spin Orbit Coupling (SOC) is introduced to molecular ab initio density matrix renormalization group (DMRG) calculations. In the presented scheme, one first approximates the electronic ground state and a number of excited states of the Born-Oppenheimer (BO) Hamiltonian with the aid of the DMRG algorithm. Owing to the spin-adaptation of the algorithm, the total spin S is a good quantum number for these states. After the non-relativistic DMRG calculation is finished, all magnetic sublevels of the calculated states are constructed explicitly, and the SOC operator is expanded in the resulting basis. To this end, spin orbit coupled energies and wavefunctions are obtained as eigenvalues and eigenfunctions of the full Hamiltonian matrix which is composed of the SOC operator matrix and the BO Hamiltonian matrix. This treatment corresponds to a quasi-degenerate perturbation theory approach and can be regarded as the molecular equivalent to atomic Russell-Saunders coupling. For the evaluation of SOC matrix elements, the full Breit-Pauli SOC Hamiltonian is approximated by the widely used spin-orbit mean field operator. This operator allows for an efficient use of the second quantized triplet replacement operators that are readily generated during the non-relativistic DMRG algorithm, together with the Wigner-Eckart theorem. With a set of spin-orbit coupled wavefunctions at hand, the molecular g-tensors are calculated following the scheme proposed by Gerloch and McMeeking. It interprets the effective molecular g-values as the slope of the energy difference between the lowest Kramers pair with respect to the strength of the applied magnetic field. Test calculations on a chemically relevant Mo complex demonstrate the capabilities of the presented method.

L-edge X-ray absorption study of mononuclear vanadium complexes and spectral predictions using a restricted open shell configuration interaction ansatz.

A series of mononuclear V((V)), V((IV)) and V((III)) complexes were investigated by V L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The spectra show significant sensitivity to the vanadium oxidation state and the coordination environment surrounding the vanadium center. The L-edge spectra are interpreted with the aid of the recently developed Density Functional Theory/Restricted Open Shell Configuration Interaction Singles (DFT/ROCIS) method. This method is calibrated for the prediction of vanadium L-edges with different hybrid density functionals and basis sets. For the B3LYP/def2-TZVP(-f) and BHLYP/def2-TZVP(-f) functional/basis-set combinations, good to excellent agreement between calculated and experimental spectra is obtained. A treatment of the spin-orbit coupling interaction to all orders is achieved by quasi-degenerate perturbation theory (QDPT), in conjunction with DFT/ROCIS for the calculation of the molecular multiplets while accounting for dynamic correlation and anisotropic covalency. The physical origin of the observed spectral features is discussed qualitatively and quantitatively in terms of spin multiplicities, magnetic sublevels and individual 2p to 3d core level excitations. This investigation is an important prerequisite for future applications of the DFT/ROCIS method to vanadium L-edge absorption spectroscopy and vanadium-based heterogeneous catalysts.

First principles calculations of the structure and V L-edge X-ray absorption spectra of V2O5 using local pair natural orbital coupled cluster theory and spin-orbit coupled configuration interaction approaches.

A detailed study of the electronic and geometric structure of V2O5 and its X-ray spectroscopic properties is presented. Cluster models of increasing size were constructed in order to represent the surface and the bulk environment of V2O5. The models were terminated with hydrogen atoms at the edges or embedded in a Madelung field. The structure and interlayer binding energies were studied with dispersion-corrected local, hybrid and double hybrid density functional theory as well as the local pair natural orbital coupled cluster method (LPNO-CCSD). Convergence of the results with respect to cluster size was achieved by extending the model to up to 20 vanadium centers. The O K-edge and the V L2,3-edge NEXAFS spectra of V2O5 were calculated on the basis of the newly developed Restricted Open shell Configuration Interaction with Singles (DFT-ROCIS) method. In this study the applicability of the method is extended to the field of solid-state catalysis. For the first time excellent agreement between theoretically predicted and experimentally measured vanadium L-edge NEXAFS spectra of V2O5 was achieved. At the same time the agreement between experimental and theoretical oxygen K-edge spectra is also excellent. Importantly, the intensity distribution between the oxygen K-edge and vanadium L-edge spectra is correctly reproduced, thus indicating that the covalency of the metal-ligand bonds is correctly described by the calculations. The origin of the spectral features is discussed in terms of the electronic structure using both quasi-atomic jj coupling and molecular LS coupling schemes. The effects of the bulk environment driven by weak interlayer interactions were also studied, demonstrating that large clusters are important in order to correctly calculate core level absorption spectra in solids.