Cooperative Sulfur Transformations at a Dinickel Site: A Metal Bridging Sulfur Radical and Its H-Atom Abstraction Thermochemistry.

Starting from the dinickel(II) dihydride complex [ML(Ni-H)2] (1M), where L3- is a bis(tridentate) pyrazolate-bridged bis(ß-diketiminato) ligand and M+ is Na+ or K+, a series of complexes [KLNi2(S2)] (2K), [MLNi2S] (3M), [LNi2(SMe)] (4), and [LNi2(SH)] (5) has been prepared. The µ-sulfido complexes 3M can be reversibly oxidized at E1/2 = -1.17 V (in THF; vs Fc+/Fc) to give [LNi2(S•)] (6) featuring a bridging S-radical. 6 has been comprehensively characterized, including by X-ray diffraction, SQUID magnetometry, EPR and XAS/XES spectroscopies, and DFT calculations. The pKa of the µ-hydrosulfido complex 5 in THF is 30.8 ± 0.4, which defines a S-H bond dissociation free energy (BDFE) of 75.1 ± 1.0 kcal mol-1. 6 reacts with H atom donors such as TEMPO-H and xanthene to give 5, while 5 reacts with 2,4,6-tri(tert-butyl)phenoxy radical in a reverse H atom transfer to generate 6. These findings provide the first full characterization of a genuine M-(µ-S•-)-M complex and provide insights into its proton-coupled electron transfer (PCET) reactivity, which is of interest in view of the prominence of M-(µ-SH/µ-S)-M units in biological systems and heterogeneous catalysis.

PINK: a tender X-ray beamline for X-ray emission spectroscopy.

A high-flux beamline optimized for non-resonant X-ray emission spectroscopy (XES) in the tender X-ray energy range has been constructed at the BESSY II synchrotron source. The beamline utilizes a cryogenically cooled undulator that provides X-rays over the energy range 2.1 keV to 9.5 keV. This energy range provides access to XES [and in the future X-ray absorption spectroscopy (XAS)] studies of transition metals ranging from Ti to Cu (Kα, Kß lines) and Zr to Ag (Lα, Lß), as well as light elements including P, S, Cl, K and Ca (Kα, Kß). The beamline can be operated in two modes. In PINK mode, a multilayer monochromator (E/ΔE ≃ 30-80) provides a high photon flux (1014 photons s-1 at 6 keV and 300 mA ring current), allowing non-resonant XES measurements of dilute substances. This mode is currently available for general user operation. X-ray absorption near-edge structure and resonant XAS techniques will be available after the second stage of the PINK commissioning, when a high monochromatic mode (E/ΔE ≃ 10000-40000) will be facilitated by a double-crystal monochromator. At present, the beamline incorporates two von Hamos spectrometers, enabling time-resolved XES experiments with time scales down to 0.1 s and the possibility of two-color XES experiments. This paper describes the optical scheme of the PINK beamline and the endstation. The design of the two von Hamos dispersive spectrometers and sample environment are discussed here in detail. To illustrate, XES spectra of phosphorus complexes, KCl, TiO2 and Co3O4 measured using the PINK setup are presented.

Probing the Local Environment in Potassium Salts and Potassium-Promoted Catalysts by Potassium Valence-to-Core X-ray Emission Spectroscopy.

Potassium plays an important role in biology as well as a promoter in heterogeneous catalysis. There are, however, limited characterization techniques for potassium available in the literature. This study elucidates the potential of element-selective X-ray emission spectroscopy (XES) for characterizing the coordination environment and the electronic properties of potassium. A series of XES measurements were conducted, primarily focusing on the VtC transition (Kß2,5) of potassium halides (KCl, KBr, and KI) and oxide-bound potassium salts, including potassium nitrate (KNO3) and potassium carbonate (K2CO3). Across the series of potassium halides, the VtC transition energy is observed to increase, as accurately reproduced by TDDFT calculations. Molecular orbital analysis suggests that the Kß2,5 transition is primarily derived from halide np contributions, with the primary factor influencing the energy shift being the metal-ligand distances. For oxide ligands, an additional Kß″ transition appears alongside the Kß2,5, which is attributed to a low-energy ligand ns, as elucidated by theoretical calculations. Finally, the XES spectra of two potassium-promoted catalysts for ammonia decomposition/synthesis were measured. These spectra show that potassium within the catalyst is distinct from other K salts in the VtC region, which could be promising for understanding the role of potassium as an electronic promoter.

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.

Cu4S Cluster in "0-Hole" and "1-Hole" States: Geometric and Electronic Structure Variations for the Active CuZ* Site of N2O Reductase.

The active site of nitrous oxide reductase (N2OR), a key enzyme in denitrification, features a unique µ4-sulfido-bridged tetranuclear Cu cluster (the so-called CuZ or CuZ* site). Details of the catalytic mechanism have remained under debate and, to date, synthetic model complexes of the CuZ*/CuZ sites are extremely rare due to the difficulty in building the unique {Cu4(µ4-S)} core structure. Herein, we report the synthesis and characterization of [Cu4(µ4-S)]n+ (n = 2, 2; n = 3, 3) clusters, supported by a macrocyclic {py2NHC4} ligand (py = pyridine, NHC = N-heterocyclic carbene), in both their 0-hole (2) and 1-hole (3) states, thus mimicking the two active states of the CuZ* site during enzymatic N2O reduction. Structural and electronic properties of these {Cu4(µ4-S)} clusters are elucidated by employing multiple methods, including X-ray diffraction (XRD), nuclear magnetic resonance (NMR), UV/vis, electron paramagnetic resonance (EPR), Cu/S K-edge X-ray emission spectroscopy (XES), and Cu K-edge X-ray absorption spectroscopy (XAS) in combination with time-dependent density functional theory (TD-DFT) calculations. A significant geometry change of the {Cu4(µ4-S)} core occurs upon oxidation from 2 (τ4(S) = 0.46, seesaw) to 3 (τ4(S) = 0.03, square planar), which has not been observed so far for the biological CuZ(*) site and is unprecedented for known model complexes. The single electron of the 1-hole species 3 is predominantly delocalized over two opposite Cu ions via the central S atom, mediated by a π/π superexchange pathway. Cu K-edge XAS and Cu/S K-edge XES corroborate a mixed Cu/S-based oxidation event in which the lowest unoccupied molecular orbital (LUMO) has a significant S-character. Furthermore, preliminary reactivity studies evidence a nucleophilic character of the central µ4-S in the fully reduced 0-hole state.

Combining Valence-to-Core X-ray Emission and Cu K-edge X-ray Absorption Spectroscopies to Experimentally Assess Oxidation State in Organometallic Cu(I)/(II)/(III) Complexes.

A series of organometallic copper complexes in formal oxidation states ranging from +1 to +3 have been characterized by a combination of Cu K-edge X-ray absorption (XAS) and Cu Kß valence-to-core X-ray emission spectroscopies (VtC XES). Each formal oxidation state exhibits distinctly different XAS and VtC XES transition energies due to the differences in the Cu Zeff, concomitant with changes in physical oxidation state from +1 to +2 to +3. Herein, we demonstrate the sensitivity of XAS and VtC XES to the physical oxidation states of a series of N-heterocyclic carbene (NHC) ligated organocopper complexes. We then extend these methods to the study of the [Cu(CF3)4]- ion. Complemented by computational methods, the observed spectral transitions are correlated with the electronic structure of the complexes and the Cu Zeff. These calculations demonstrate that a contraction of the Cu 1s orbitals to deeper binding energy upon oxidation of the Cu center manifests spectroscopically as a stepped increase in the energy of both XAS and Kß2,5 emission features with increasing formal oxidation state within the [Cun+(NHC2)]n+ series. The newly synthesized Cu(III) cation [CuIII(NHC4)]3+ exhibits spectroscopic features and an electronic structure remarkably similar to [Cu(CF3)4]-, supporting a physical oxidation state assignment of low-spin d8 Cu(III) for [Cu(CF3)4]-. Combining XAS and VtC XES further demonstrates the necessity of combining multiple spectroscopies when investigating the electronic structures of highly covalent copper complexes, providing a template for future investigations into both synthetic and biological metal centers.

Ruthenium 4d-to-2p X-ray Emission Spectroscopy: A Simultaneous Probe of the Metal and the Bound Ligands.

Ruthenium 4d-to-2p X-ray emission spectroscopy (XES) was systematically explored for a series of Ru2+ and Ru3+ species. Complementary density functional theory calculations were utilized to allow for a detailed assignment of the experimental spectra. The studied complexes have a range of different coordination spheres, which allows the influence of the ligand donor/acceptor properties on the spectra to be assessed. Similarly, the contributions of the site symmetry and the oxidation state of the metal were analyzed. Because the 4d-to-2p emission lines are dipole-allowed, the spectral features are intense. Furthermore, in contrast with K- or L-edge X-ray absorption of 4d transition metals, which probe the unoccupied levels, the observed 4p-to-2p XES arises from electrons in filled-ligand- and filled-metal-based orbitals, thus providing simultaneous access to the ligand and metal contributions to bonding. As such, 4d-to-2p XES should be a promising tool for the study of a wide range of 4d transition-metal compounds.

Orbit and spin resolved magnetic properties of size selected [ConRh]⁺ and [ConAu]⁺ nanoalloy clusters.

Bi-metallic nanoalloys of mixed 3d-4d or 3d-5d elements are promising candidates for technological applications. The large magnetic moment of the 3d materials in combination with a high spin-orbit coupling of the 4d or 5d materials give rise to a material with a large magnetic moment and a strong magnetic anisotropy, making them ideally suitable in for example magnetic storage devices. Especially for clusters, which already have a higher magnetic moment compared to the bulk, these alloys can profit from the cooperative role of alloying and size reduction in order to obtain magnetically stable materials with a large magnetic moment. Here, the influence of doping of small cobalt clusters on the spin and orbital magnetic moment has been studied for the cations [Co(8-14)Au](+) and [Co(10-14)Rh](+). Compared to the undoped pure cobalt [Co(N)](+) clusters we find a significant increase in the spin moment for specific Co(N-1)Au(+) clusters and a very strong increase in the orbital moment for some Co(N-1)Rh(+) clusters, with more than doubling for Co12Rh(+). This result shows that substitutional doping of a 3d metal with even just one atom of a 4d or 5d metal can lead to dramatic changes in both spin and orbital moment, opening up the route to novel applications.

The spin and orbital contributions to the total magnetic moments of free Fe, Co, and Ni clusters.

We present size dependent spin and orbital magnetic moments of cobalt (Con (+), 8 ≤ n ≤ 22), iron (Fen (+), 7 ≤ n ≤ 17), and nickel cluster (Nin (+), 7 ≤ n ≤ 17) cations as obtained by X-ray magnetic circular dichroism (XMCD) spectroscopy of isolated clusters in the gas phase. The spin and orbital magnetic moments range between the corresponding atomic and bulk values in all three cases. We compare our findings to previous XMCD data, Stern-Gerlach data, and computational results. We discuss the application of scaling laws to the size dependent evolution of the spin and orbital magnetic moments per atom in the clusters. We find a spin scaling law "per cluster diameter," ∼n(-1/3), that interpolates between known atomic and bulk values. In remarkable contrast, the orbital moments do likewise only if the atomic asymptote is exempt. A concept of "primary" and "secondary" (induced) orbital moments is invoked for interpretation.

Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal-organic framework.

In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O2 to form high-spin iron(IV) = O species remains an unrealized goal. Here, we report a metal-organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases. The framework reacts with O2 at low temperatures to form high-spin iron(IV) = O species that are characterized using in situ diffuse reflectance infrared Fourier transform, in situ and variable-field Mössbauer, Fe Kß x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O2, the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.

Phosphorus Kß X-ray emission spectroscopy detects non-covalent interactions of phosphate biomolecules in situ.

Phosphorus is ubiquitous in biochemistry, being found in the phosphate groups of nucleic acids and the energy-transferring system of adenine nucleotides (e.g. ATP). Kß X-ray emission spectroscopy (XES) of phosphorus has been largely unexplored, with no previous applications to biomolecules. Here, the potential of P Kß XES to study phosphate-containing biomolecules, including ATP and NADPH, is evaluated, as is the application of the technique to aqueous solution samples. P Kß spectra offer a detailed picture of phosphate valence electronic structure, reporting on subtle non-covalent effects, such as hydrogen bonding and ionic interactions, that are key to enzymatic catalysis. Spectral features are interpreted using density functional theory (DFT) calculations, and potential applications to the study of biological energy conversion are highlighted.

Evolution of metallic screening in small metal clusters probed by PCI-Auger spectroscopy.

Excitation-energy dependent Auger spectra of small copper clusters supported by a thin silica layer have been measured as function of cluster size. The Auger kinetic energy of the clusters clearly changes with the excess energy of the emitted photoelectron while not for the bulk. The kinetic energy shift is attributed to post-collision interaction (PCI) and exhibits a reduced metallic screening ability of small Cu-clusters. The spectroscopic data reveal an evolution from a long-range Coulomb-like interaction to a short-range "screened" electrostatic interaction within the sub-nm range. The data show that core electron spectroscopy such as PCI-Auger measurements can be used as a general tool to follow the metallic character of supported clusters.