Diketiminate-supported iron complexes are capable of cleaving the strong triple bond of N2 to give a tetra-iron complex with two nitrides (Rodriguez et al., Science, 2011, 334, 780-783). The mechanism of this reaction has been difficult to determine, but a transient green species was observed during the reaction that corresponds to a potential intermediate. Here, we describe studies aiming to identify the characteristics of this intermediate, using a range of spectroscopic techniques, including Mössbauer spectroscopy, electronic absorption spectroscopy, Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and nuclear resonance vibrational spectroscopy (NRVS) complemented by density functional theory (DFT) calculations. We successfully elucidated the nature of the starting iron(II) species and the bis(nitride) species in THF solution, and in each case, THF breaks up the multiiron species. Various observations on the green intermediate species indicate that it has one N2 per two Fe atoms, has THF associated with it, and has NRVS features indicative of bridging N2. Computational models with a formally diiron(0)-N2 core are most consistent with the accumulated data, and on this basis, a mechanism for N2 splitting is suggested. This work shows the power of combining NRVS, Mössbauer, NMR, and vibrational spectroscopies with computations for revealing the nature of transient iron species during N2 cleavage.
The biological conversion of N2 to NH3 is accomplished by the nitrogenase family, which is collectively comprised of three closely related but unique metalloenzymes. In the present study, we have employed a combination of the synchrotron-based technique of 57Fe nuclear resonance vibrational spectroscopy together with DFT-based quantum mechanics/molecular mechanics (QM/MM) calculations to probe the electronic structure and dynamics of the catalytic components of each of the three unique M N2ase enzymes (M = Mo, V, Fe) in both the presence (holo-) and absence (apo-) of the catalytic FeMco clusters (FeMoco, FeVco and FeFeco). The results described herein provide vibrational mode assignments for important fingerprint regions of the FeMco clusters, and demonstrate the sensitivity of the calculated partial vibrational density of states (PVDOS) to the geometric and electronic structures of these clusters. Furthermore, we discuss the challenges that are faced when employing NRVS to investigate large, multi-component metalloenzymatic systems, and outline the scope and limitations of current state-of-the-art theory in reproducing complex spectra.
Nitrogenase , Nitrogenase/chemistry , Catalytic Domain , Spectrum Analysis
Ferropericlase (Mg,Fe)O is the second most abundant mineral in Earth's lower mantle and a common inclusion found in subcratonic diamonds. Pyrolitic mantle has Mg# (100 × Mg/(Mg+Fe)) ~89. However, ferropericlase inclusions in diamonds show a broad range of Mg# between 12 and 93. Here we use Synchrotron Mössbauer Source (SMS) spectroscopy and single-crystal X-ray diffraction to determine the iron oxidation state and structure of two magnesiowüstite and three ferropericlase inclusions in diamonds from São Luiz, Brazil. Inclusion Mg#s vary between 16.1 and 84.5. Ferropericlase inclusions contain no ferric iron within the detection limit of SMS, while both magnesiowüstite inclusions show the presence of monocrystalline magnesioferrite ((Mg,Fe)Fe3+2O4) with an estimated 47-53 wt% Fe2O3. We argue that the wide range of Fe concentrations observed in (Mg,Fe)O inclusions in diamonds and the appearance of magnesioferrite result from oxidation of ferropericlase triggered by the introduction of subducted material into sublithospheric mantle.
α-Sb2O3 (senarmontite), ß-Sb2O3 (valentinite), and α-TeO2 (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here, we present a study of the relationship between bonding and lattice dynamics of these compounds. Mössbauer spectroscopy is used to study the structure of Sb in α-Sb2O3 and ß-Sb2O3, whereas the vibrational modes of Sb and Te for each oxide are investigated using nuclear inelastic scattering, and further information on O vibrational modes is obtained using inelastic neutron scattering. Additionally, vibrational frequencies obtained by density functional theory (DFT) calculations are compared with experimental results in order to assess the validity of the utilized functional. Good agreement was found between DFT-calculated and experimental density of phonon states with a 7% scaling factor. The Sb-O-Sb wagging mode of α-Sb2O3 whose frequency was not clear in most previous studies is experimentally observed for the first time at â¼340 cm-1. Softer lattice vibrational modes occur in orthorhombic ß-Sb2O3 compared to cubic α-Sb2O3, indicating that the antimony bonds are weakened upon transforming from the molecular α phase to the layer-chained ß structure. The resulting vibrational entropy increase of 0.45 ± 0.1 kB/Sb2O3 at 880 K accounts for about half of the α-ß transition entropy. The comparison of experimental and theoretical approaches presented here provides a detailed picture of the lattice dynamics in these oxides beyond the zone center and shows that the accuracy of DFT is sufficient for future calculations of similar material structures.
Hard-x-ray spectroscopy relies on a suite of modern techniques for studies of vibrational, electronic, and magnetic excitations in condensed matter. At present, the energy resolution of these techniques can be improved only by decreasing the spectral window of the involved optics-monochromators and analyzers-thereby sacrificing the intensity. Here, we demonstrate hard-x-ray spectroscopy with greatly improved energy resolution without narrowing the spectral window by adapting principles of spectrographic imaging to the hard-x-ray regime. Similar to Newton's classical prism, the hard-x-ray spectrograph disperses different "colors"-i.e., energies-of x-ray photons in space. Then, selecting each energy component with a slit ensures high energy resolution, whereas measuring x-ray spectra with all components of a broad spectral window keeps the intensity. We employ the principles of spectrographic imaging for phonon spectroscopy. Here the new approach revealed anomalous soft atomic dynamics in α-iron, a phenomenon which was not previously reported in the literature. We argue that hard-x-ray spectrographic imaging also could be a path to discovering new physics in studies of electronic and magnetic excitations.
Spin-crossover nanomaterials have been actively studied in the past decade for their potential technological applications in sensing, actuating, and information processing devices. Unfortunately, an increasing number of the metallic centers become inactive at reduced sizes, presumably due to surface effects, limiting their switching ability and thus the scope of applications. Here we report on the investigation of "frozen" metallic centers in nanoparticles (2-80 nm size) of the spin-crossover compound Fe(pyrazine)[Ni(CN)4]. Magnetic measurements reveal both high-spin and low-spin residual fractions at atmospheric pressure. A pressure-induced transition of the high-spin residue is observed at around 1.5 GPa by synchrotron Mössbauer spectroscopy. We show that it is equivalent to a downshift of the transition temperature by ca. 400 K due to the size reduction. Unexpectedly, small-angle neutron scattering experiments demonstrate that these high-spin residual centers are not confined to the surface, which contradicts general theoretical considerations.
The lattice dynamics in an array of 56 nm diameter Bi2Te3 nanowires embedded in a self-ordered amorphous alumina membrane were investigated microscopically using (125)Te nuclear inelastic scattering. The element specific density of phonon states is measured on nanowires in two perpendicular orientations and the speed of sound is extracted. Combined high energy synchrotron radiation diffraction and transmission electron microscopy was carried out on the same sample and the crystallinity was investigated. The nanowires grow almost perpendicular to the c-axis, partly with twinning. The average speed of sound in the 56 nm diameter Bi2Te3 nanowires is ~7% smaller with respect to bulk Bi2Te3 and a decrease in the macroscopic lattice thermal conductivity by ~13% due to nanostructuration and to the reduced speed of sound is predicted.
Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 Mössbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C.
