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Sattelberger, Alfred P.

Publications and source records attributed to Sattelberger, Alfred P..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Electrochemical Investigation of Low-Valent Multiply M≡M Bonded Group VI Dimers: A Standard Chemical Reduction Leads to an Unexpected Product

The synthesis and investigation of multimetallic complexes bearing metal–metal bonds have been significantly advanced over the last 30 years with exciting applications across many fields. While the outlook for synthetically innovative metal–metal species is promising, the reactivity of the classic M 2 X 6 alkyl dimers (where M = W, Mo; X = CH 2 CMe 3 , CH 2 SiMe 3 ) is still not fully understood. In particular, the redox characteristics of these complexes have not been explored by cyclic voltammetry (CV). In this work, W 2 (CH 2 CMe 3 ) 6 and Mo 2 (CH 2 CMe 3 ) 6 (1 and 2, respectively) were characterized using CV to show differing electrochemical behavior between the two species. Stoichiometric reactions, guided by the results of the CV experiments, led to the isolation of an alkylidyne-bridged dimer bearing a rare structural motif, W 2 (μ-CCMe 3 ) 2 (CH 2 CMe 3 ) 4 (3). Single-crystal X-ray diffraction (SCXRD) and 1 H and 13 C nuclear magnetic resonance spectroscopy (NMR) were used to establish the connectivity of the structure in the solid and solution phases. Density functional theory (DFT) calculations on 1–3 and the previously reported W 2 (CSiMe 3 ) 2 (CH 2 SiMe 3 ) 4 (4) were used to rationalize the reactivity of 1 to form 3 and the structural differences between 3 and 4. Complexes 3 and 4 constitute a case in which the stereoelectronic properties of the silyl neopentyl ligand can affect differences in structure and bonding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Atomic layer deposition of HfO 2 films using carbon-free tetrakis(tetrahydroborato)hafnium and water

Thin hafnium oxide films were prepared by atomic layer deposition using a carbon-free precursor, tetrakis(tetrahydroborato)hafnium [Hf(BH 4 )( 4 )], and H 2 O. Film growth was studied using an in situ quartz crystal microbalance and Fourier transform infrared spectroscopy measurements. Self-limiting growth was observed between 100 and 175 degrees C, but the thermal decomposition of the Hf precursor occurred at higher temperatures. The film properties were investigated using x-ray photoelectron spectroscopy, x-ray reflectivity, x-ray diffraction, ellipsometry, time-of-flight secondary ion mass spectrometry, and x-ray absorption spectroscopy. The as-deposited films were found to consist of an amorphous mixture of HfO 2 and B 2 O 3 , and had a lower density and lower refractive index compared to pure HfO 2 thin films. Finally, annealing the films to >750 degrees C yielded crystalline monoclinic HfO 2 with a density of 9g/cm 3 and a refractive index of 2.10.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Solvothermal synthesis and solid-state characterization of metal-metal bonded tetracarboxylatoditechnetium(II,III) polymers

Investigations of solvothermal reactions with pertechnetate, [TcO 4 ] - , have produced four new low-valent Tc extended metal atom chain (EMAC) complexes with multiple metal-metal bonds. The thermal reaction of potassium pertechnetate with glacial acetic acid, under in-situ hydrogen production from the decomposition of sodium borohydride, yields purple elongated crystals determined to be tetraacetato ditechnetium (II,III) acetate (1), [Tc 2 (O 2 CCH 3 ) 4 (μ-O 2 CCH 3 ] n . Compound 1 was characterized by single crystal X-ray diffraction and its magnetic properties recorded between 10 and 300 K. Single crystal X-ray diffraction analysis of 1 indicates the Tc 2 +5 tetraacetato unit is linked by the carboxylate oxygens of the bridging acetate, similar to known chloride and bromide linkage polymers of composition [Tc 2 (μ-O 2 CCH 3 ) 4 Cl] n , and [Tc 2 (μ-O 2 CCH 3 ) 4 Br] n . Here, using the same synthetic method three similar compounds have been synthesized from propionic, benzoic and pivalic acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry

Olefin metathesis is a broadly employed reaction with applications that range from fine chemicals to materials and petrochemicals. The design and investigation of olefin metathesis catalysts have been ongoing for over half a century, with advancements made in terms of activity, stability, and selectivity. Immobilization of organometallic complexes onto solid supports such as silica or alumina is a promising strategy for catalyst heterogenization, often resulting in increased activity and stability. Consequently, a broad range of early transition metal catalysts bearing alkyl, oxide/alkoxide, and amide ligands have been grafted onto silica and their reactivities investigated. In this paper, we report a series of silica-supported tungsten and molybdenum dimers (X 3 M≡MX 3, where M = W and Mo; X = neopentyl, tert-butoxide, and dimethyl amide) and their reactivities toward catalytic olefin metathesis. Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR), diffuse reflectance infrared Fourier transform (DRIFT), UV resonance Raman, and X-ray absorption (XAS) spectroscopies suggest that upon heterogenization the dimers bind to the surface in a monopodal fashion, with the M≡M triple bond remaining intact. These structural assignments were further corroborated by density functional theory (DFT) calculations. While the homogeneous dimer counterparts are inert, the supported low-valent alkyl W and Mo dimers become active for the disproportionative self-metathesis of propylene to ethylene and butenes and 4-nonene to 4-octene and 5-decene under mild conditions. The lack of activity observed for the free and supported tert-butoxide and dimethyl amide dimers likely suggests that the neopentyl groups are necessary for the formation of a putative alkylidene active species. The difference in reactivity between the free and supported dimers could be explained either by the lowering of the activation barrier of the complex through the electronic effects of the surface or by site isolation of catalytically relevant reactive intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Formation of Unsaturated Hydrocarbons and Hydrogen: Surface Chemistry of Methyltrioxorhenium(VII) in ALD of Mixed-Metal Oxide Structures Comprising Re(III) Units

We present the full investigation of the atomic layer deposition (ALD) of a mixed rhenium-aluminum oxide, namely ReAl 2 O 3 CH 3 , a material with tunable resistance, comprising the building unit of conductive rhenium oxides, ReOx. The deposition, involving methyltrioxorhenium(VII) (MeReO 3 , MTO) and trimethylaluminum (TMA), was analyzed by employing complementary in situ diagnostic quartz-crystal microbalance (QCM), Fourier-transform infrared (FT-IR) spectroscopy, and quadrupole mass spectrometry (QMS) to explore and reveal the underlying growth mechanism of this material. A proposed mechanism includes reductive elimination steps, thereby creating a stable Re(III)-containing thin film, making this ALD process unique regarding its growth. In addition, as proven by QMS, the surface reactions include the formation of hydrogen and unsaturated hydrocarbons. From this straightforward process, an extraordinarily high growth rate of 4.5 angstrom cycle -1 at temperatures as low as 150 °C was obtained. This material was found to exhibit highly promising electrical properties in terms of low thermal coefficient of resistance (TCR) in combination with high resistivity. By blending thin films of ReAl 2 O 3 CH 3 with additional layers (1, 2, or 3) of Al 2 O 3 , we were able to fine-tune the electrical resistivity in the range of 3.9 x 10(6) -1.5 x 10 11 Ω.cm. Simultaneously, the TCR was lowered to about -0.014 degrees °C -1 , making this material highly resistive over a broad temperature range and a promising candidate for advanced detector applications, e.g., multichannel plates (MCPs).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Catalytic Applications of Vanadium: A Mechanistic Perspective

The chemistry of vanadium has seen remarkable activity in the past SO years. In the present review, reactions catalyzed by homogeneous and supported vanadium complexes from 2008 to 2018 are summarized and discussed. Here particular attention is given to mechanistic and kinetics studies of vanadium-catalyzed reactions including oxidations of alkanes, alkenes, arenes, alcohols, aldehydes, ketones, and sulfur species, as well as oxidative C-C and C-O bond cleavage, carbon carbon bond formation, deoxydehydration, haloperoxidase, cyanation, hydrogenation, dehydrogenation, ring-opening metathesis polymerization, and oxo/imido heterometathesis. Additionally, insights into heterogeneous vanadium catalysis are provided when parallels can be drawn from the homogeneous literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Nuclearity effects in supported, single-site Fe( ii ) hydrogenation pre-catalysts

Dimeric and monomeric supported single-site Fe(II) pre-catalysts on SiO 2 have been prepared via organometallic grafting and characterized with advanced spectroscopic techniques. Manipulation of the surface hydroxyl concentration on the support influences monomer/dimer formation. While both pre-catalysts are highly active in liquid-phase hydrogenation, the dimeric pre-catalyst is ~3× faster than the monomer. Here, preliminary XAS experiments on the H 2 -activated samples suggest the active species are isolated Fe(II) sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

The Nature of the Technetium Species Formed During the Oxidation of Technetium Dioxide with Oxygen and Water

The oxidation of TcO 2 with O 2 in the presence of H 2 O at 250 °C was investigated; Tc 2 O 7 and a red product were observed after the reaction. UV/Visible spectroscopy and a cerium titration on the “red” product are consistent with the presence of a reduced Tc species. It is proposed that the “red” product was formed by the hydrolysis of Tc 2 O 7 to HTcO 4 followed by the reduction of HTcO 4 . The reaction products of TcO 2 with O 2 /H 2 O at 250 °C were also studied by mass spectrometry. The main dinuclear species were Tc 2 O 7 and Tc 2 O 5 , while the main mononuclear species were TcO 3 and HTcO 4 . The compound HTcO 4 and associated hydrates were simulated to identify candidate structures for the “red” product; however, neither the acid nor any related hydrates exhibited the UV/Visible signature of the “red” product.

Childs, Bradley C.↗
DOE OSTI2017

Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2 L 4 F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp – ); 2, L = diphenyl formamidinate (dpf – )) were prepared from the solid-state melt reactions (SSMRs) between (NH 4 ) 2 [Re 2 F 8 ]·2H 2 O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2 (hpp) 4 F 2 ]PF 6 (3) was prepared from the one-electron oxidation of Re 2 (hpp) 4 F 2 with [Cp 2 Fe]PF 6 . Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoes two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2 (hpp) 4 F 2 (1) is more easily oxidized than its chloro and bromo analogues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Molecular and electronic structures of M 2 O 7 (M = Mn, Tc, Re)

The molecular and electronic structures for the Group 7b heptoxides were investigated by computational methods as both isolated molecules and in the solid-state. The metal-oxygen-metal bending angle of the single molecule increased with increasing atomic number, with Re 2 O 7 preferring a linear structure. Natural bond orbital and localized orbital bonding analyses indicate that there is a three-center covalent bond between the metal atoms and the bridging oxygen, and the increasing ionic character of the bonds favors larger bond angles. The calculations accurately reproduce the experimental crystal structures within a few percent. Analysis of the band structures and density of states shows similar bonding for all of the solid-state heptoxides, including the presence of the three-center covalent bond. DFT+U simulations show that PBE-D3 underpredicts the band gap by ~0.2 eV due to an under-correlation of the metal d conducting states. As a result, homologue and compression studies show that Re 2 O 7 adopts a polymeric structure because the Re-oxide tetrahedra are easily distorted by packing stresses to form additional three-center covalent bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Technetium: The First Radioelement on the Periodic Table

The radioactive nature of technetium is discussed using a combination of introductory nuclear physics concepts and empirical trends observed in the chart of the nuclides and the periodic table of the elements. Trends such as the enhanced stability of nucleon pairs, magic numbers, and Mattauch's rule are described. Here, the concepts of nuclear binding energies and the nuclear shell model are introduced and used to explain the relative stability of radionuclides and, in particular, the isotopes of technetium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies

Here, ditechnetium heptoxide was synthesized from the oxidation of TcO 2 with O 2 at 450 °C and characterized by single crystal X-ray diffraction (SCXRD), electron impact mass spectrometry (EI-MS) and theoretical methods. Refinement of the structure at 100 K indicates that Tc 2 O 7 crystallizes as a molecular solid in the orthorhombic space group Pbca (a = 7.312(3) Å, b = 5.562(2) Å, c = 13.707(5) Å, V = 557.5(3) Å 3 ). The Tc 2 O 7 molecule can be described as corner-sharing TcO4 tetrahedra (Tc---Tc = 3.698(1) Å and Tc-O Bri -Tc = 180.0°). The EI-MS spectrum of Tc 2 O 7 consists of both mononuclear and dinuclear species. The main dinuclear species in the gas-phase are Tc 2 O 7 (100%) and Tc 2 O 5 (56%), while the main mononuclear species are TcO 3 (33.9%) and TcO 2 (42.8%). The difference in the relative intensities of the M 2 O 5 (M = Tc, Re) fragments (1.7% for Re) indicate that these Group 7 elements exhibit different gas phase chemistry. The solid-state structure of Tc 2 O 7 was investigated by density functional theory (DFT) methods. The optimized structure of the Tc 2 O 7 molecule is in good agreement with the experimental one. Simulations indicate that the more favorable geometry for the Tc 2 O 7 molecule in the gas-phase is bent (Tc-O Bri -Tc = 156.5°), while linear (Tc-O Bri -Tc = 180.0°) is favored in the solid state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Photochemical behavior of the quadruply metal-metal bonded [Tc 2 Cl 8 ] 2– anion in acetonitrile

Here, the photochemical behavior of [Tc 2 Cl 8 ] 2– was investigated in acetonitrile. The speciation of Tc before and after irradiation at 254 nm was performed by UV-visible spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Upon irradiation at 254 nm, [Tc 2 Cl 8 ] 2– was unstable, the scission of the Tc ≡ Tc unit occurred and the complex [TcCl 4 (CH 3 CN) 2 ] was identified. The disappearance rate of [M 2 Cl 8 ] 2– (M = Tc, Re) under irradiation has been measured and was ~7.5 time faster for Tc than for Re.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Molecular and electronic structure of Re 2 Br 4 (PMe 3 ) 4

The dinuclear rhenium(II) complex Re 2 Br 4 (PMe 3 ) 4 was prepared from the reduction of [Re 2 Br 8 ] 2– with ( n -Bu 4 N)BH 4 in the presence of PMe 3 in propanol. The complex was characterized by single-crystal X-ray diffraction (SCXRD) and UV–visible spectroscopy. It crystallizes in the monoclinic C2/c space group and is isostructural with its molybdenum and technetium analogues. The Re–Re distance (2.2521(3) Å) is slightly longer than the one in Re 2 Cl 4 (PMe 3 ) 4 (2.247(1) Å). The molecular and electronic structure of Re 2 X 4 (PMe 3 ) 4 (X = Cl, Br) were studied by multiconfigurational quantum chemical methods. The computed ground-state geometry is in excellent agreement with the experimental structure determined by SCXRD. The calculated total bond order (2.75) is consistent with the presence of an electron-rich triple bond and is similar to the one found for Re 2 Cl 4 (PMe 3 ) 4 . The electronic absorption spectrum of Re 2 Br 4 (PMe 3 ) 4 was recorded in benzene and shows a series of low-intensity bands in the range 10 000–26 000 cm –1 . The absorption bands were assigned based on calculations of the excitation energies with the multireference wave functions followed by second-order perturbation theory using the CASSCF/CASPT2 method. As a result, calculations predict that the lowest energy band corresponds to the δ* → σ* transition, while the next higher energy bands were attributed to the δ* → π*, δ → σ*, and δ → π* transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Structural Properties of Ditechnetium Heptoxide, Tc{sub 2}O{sub 7}

Group 7 elements form unique binary oxides with the stoichiometry M{sub 2}O{sub 7}. The heptoxides of manganese and technetium crystallize as molecular solids while rhenium forms an extended solid with mixed valances, 4 and 6. Unlike manganese and rhenium heptoxides which are used in the chemical industry technetium heptoxide has found very few applications due to its radioactive nature; it has been primarily use as a chemical precursor. While both of the molecular solids, Mn{sub 2}O{sub 7}{sup 3} and Tc{sub 2}O{sub 7}{sup 4} can be described by two corner-sharing MO{sub 4} tetrahedron. The most distinctive difference is that the manganese's compound has a metal-oxygen-metal bond angle of 120.7 deg. while the technetium species is 180 deg.. Additionally, Tc{sub 2}O{sub 7} has the largest molar volume of the heptoxides which suggest that it will be more susceptible to external stimuli of pressure and temperature than the others heptoxides. A pressure induced twisting has been predicted by Fang et al. Anomalous behavior is seen in the c-axis where below 2 GPa the Van der Waals interactions between the Tc{sub 2}O{sub 7} molecules is over come and compression is observed but at higher pressures the twisted distortion forces the lattice to expand. The terminology diagonal-double tetrahedrons (DDTs) is introduced to discuss the molecules of Tc{sub 2}O{sub 7}. The rigid nature of the DDTs has been attributed to the cause of this twisted distortion mechanism. Recently, the solid state and gas phase behavior of technetium heptoxide was revisited by Childs et al. in light of {sup 99}Tc being an important dose contributor in the Hanford waste and vitrification being proposed for immobilization of nuclear waste. Technetium heptoxide is one of the proposed volatilized species of technetium found in the vitrification process. In this study the crystal structure of Tc{sub 2}O{sub 7} was reported at 100 K and compared to the structure first determined by Krebs at room temperature. Inspection of the metal-oxygen distances revealed the 100 K structure had longer bond lengths for the bridging oxygen than at high temperature. It is suggested that transverse thermal vibrational modes can be used to explain this negative thermal expansion behavior. This describes the average bond length of a central atom (i.e. the bridging oxygen atom) being measured as shorter at higher temperatures due to the larger thermal motion. Diffraction methods that measure the long range average structure are susceptible to observing this shorter average length as opposed to the true bond length, atom position at oscillation node that a method like Pair-Distribution Functional PDF Analysis would yield. In the case of Tc{sub 2}O{sub 7}, the magnitude of the transverse thermal vibrational mode is at the limit of being detectable by SCXRD and likely not observable by PDF analysis. Here we report the preliminary results of our study on the nature of the thermal expansion behavior of Tc{sub 2}O{sub 7}. The transverse thermal vibration mode compression mechanism is considered and compared to the pressure induced twisted distortion mechanism predicted at high pressure. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Octafluorodirhenate(III) Revisited: Solid-State Preparation, Characterization, and Multiconfigurational Quantum Chemical Calculations

A simple method for the high-yield preparation of (NH 4 ) 2 [Re 2 F 8 ]· 2H 2 O has been developed that involves the reaction of (n-Bu 4 N)2[Re 2 Cl 8 ] with molten ammonium bifluoride (NH 4 HF 2 ). Using this method, the new salt [NH 4 ] 2 [Re 2 F 8 ]·2H 2 O was prepared in ~90% yield. The product was characterized in solution by ultraviolet-visible light (UV-vis) and 19 F nuclear magnetic resonance (19F NMR) spectroscopies and in the solid-state by elemental analysis, powder X-ray diffraction (XRD), and infrared (IR) spectroscopy. Multiconfigurational CASSCF/CASPT2 quantum chemical calculations were performed to investigate the molecular and electronic structure, as well as the electronic absorption spectrum of the [Re 2 F 8 ] 2- anion. The metal-metal bonding in the Re 2 6+ unit was quantified in terms of effective bond order (EBO) and compared to that of its [Re 2 Cl 8 ] 2- and [Re 2 Br 8 ] 2- analogues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗