Molybdenum(III) Amidinate: Synthesis, Characterization, and Vapor Phase Growth of Mo-Based Materials.

The synthesis, characterization, and thermogravimetric analysis of tris(N,N'-di-isopropylacetamidinate)molybdenum(III), Mo(iPr-AMD)3, are reported. Mo(iPr-AMD)3 is a rare example of a homoleptic mononuclear complex of molybdenum(III) and fills a longstanding gap in the literature of transition metal(III) trisamidinate complexes. Thermogravimetric analysis (TGA) reveals excellent volatilization at elevated temperatures, pointing to potential applications as a vapor phase precursor for higher temperature atomic layer deposition (ALD), or chemical vapor deposition (CVD) growth of Mo-based materials. The measured TGA temperature window was 200-314 °C for samples in the 3-20 mg range. To validate the utility of Mo(iPr-AMD)3, we demonstrate aerosol-assisted CVD growth of MoO3 from benzonitrile solutions of Mo(iPr-AMD)3 at 500 °C using compressed air as the carrier gas. The resulting films are characterized by X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy. We further demonstrate the potential for ALD growth at 200 °C with a Mo(iPr-AMD)3/Ar purge/300 W O2 plasma/Ar purge sequence, yielding ultrathin films which retain a nitride/oxynitride component. Our results highlight the broad scope utility and potential of Mo(iPr-AMD)3 as a stable, high-temperature precursor for both CVD and ALD processes.

Binding Small Molecules to a cis-Dicarbonyl 99TcI-PNP Complex via Metal-Ligand Cooperativity.

Metal-ligand cooperativity is a powerful tool for the activation of various bonds but has rarely, if ever, been studied with the radioactive transition metal 99Tc. In this work, we explore this bond activation pathway with the dearomatized PNP complex cis-[99TcI(PyrPNPtBu*)(CO)2] (4), which was synthesized by deprotonation of trans-[99TcI(PyrPNPtBu)(CO)2Cl] with KOtBu. Analogous to its rhenium congener, the dearomatized compound reacts with CO2 to form the carboxy complex cis-[99TcI(PyrPNPtBu-COO)(CO)2] and with H2 to form the mono-hydride complex cis-[99TcI(PyrPNPtBu)(CO)2H] (7). Substrates with weakly acidic protons are deprotonated by the Brønsted basic pincer backbone of 4, yielding a variety of intriguing complexes. Reactions with terminal alkynes enable the isolation of acetylide complexes. The deprotonation of an imidazolium salt results in the in situ formation and coordination of a carbene ligand. Furthermore, a study with heterocyclic substrates allowed for the isolation of pyrrolide and pyrazolide complexes, which is uncommon for Tc. The spectroscopic analyses and their solid-state structures are reported.

Synthesis, characterization, X-ray and electronic structures of diethyl ether and 1,2-dimethoxyethane adducts of molybdenum(IV) chloride and tungsten(IV) chloride.

The bis(diethyl ether) and 1,2-dimethoxyethane (dme) adducts of molybdenum(IV) chloride and tungsten(IV) chloride are valuable starting materials for a variety of synthetic inorganic and organometallic reactions. Despite the broad utility and extensive use of these 6-coordinate complexes, their syntheses remain unoptimized, and their characterization incomplete after more than three decades. While exploring the ligand exchange behaviour of trans-MoCl4(OEt2)2, we obtained single crystals of this red-orange complex and subsequently compared its structural parameters with those of the recently reported trans-WCl4(OEt2)2. Significantly improved procedures for both MoCl4(dme) and WCl4(dme) were developed, and X-ray diffraction data were obtained and analysed. The magnetic properties of the dme adducts were probed, both with Gouy and SQUID magnetometry measurements. The magnetic moment of WCl4(dme) was smaller than that of MoCl4(dme), an observation that we attribute to the greater spin-orbit coupling of tungsten. Electronic structure studies were also conducted to probe the preferential trans configuration of the diethyl ether adducts and to assign the UV-Vis spectra of the dme adducts.

Electronic Structure of Re2(O2CR)4Cl2 Complexes (R = H, CMe3) and Reassignment of the Electronic Absorption Spectrum of Re2(O2CCMe3)4Cl2.

Electronic structure calculations on two dinuclear rhenium(III) carboxylate complexes, Re2(O2CH)4Cl2 and Re2(O2CCMe3)4Cl2, are presented and discussed. Allowed electronic transitions for both molecules were calculated using time-dependent density functional theory (TDDFT). The results for the pivalate dimer, Re2(O2CCMe3)4Cl2, are compared with previously reported single-crystal polarized absorption spectra obtained by Martin and co-workers (Inorg. Chem.1984, 23, 699-701). Several revisions to the previous spectral assignments are proposed.

"MoCl3(dme)" Revisited: Improved Synthesis, Characterization, and X-ray and Electronic Structures.

"MoCl3(dme)" (dme = 1,2-dimethoxyethane) is an important precursor for midvalent molybdenum chemistry, particularly for triply Mo-Mo bonded compounds of the type Mo2X6 (X = bulky anionic ligand). However, its exact structural identity has been obscure for more than 50 years. In search of a convenient, large-scale synthesis, we have found that trans-MoCl4(Et2O)2 dissolved in dme can be cleanly reduced with dimethylphenylsilane, Me2PhSiH, to provide khaki Mo2Cl6(dme)2 in ∼90% yield. If the reduction is performed on a small scale, single crystals suitable for X-ray crystallography can be obtained. Two different crystal morphologies were identified, each belonging to the P21/n space group, but with slightly different unit cell constants. The refined structure of each form is an edge-shared bioctahedron with overall Ci symmetry and metal-metal separations on the order of 2.8 Å. The bulk material is diamagnetic as determined by both the Gouy method and SQUID magnetometry. Density functional theory calculations suggest a σ2π2δ*2 ground state for the dimer with the diamagnetism arising from a singlet diradical "broken symmetry" electronic configuration. In addition to a definitive structural assignment for "MoCl3(dme)", this work highlights the utility of organosilanes as easy to handle, alternative reductants for inorganic synthesis.

A 35-year-old mystery solved: a facile synthetic route and structural confirmation of tetrachlorobis(diethyl ether)tungsten(IV).

The true identity of the diethyl ether adduct of tungsten(IV) chloride, WCl4(Et2O)x, has been in doubt since 1985. Initially postulated as the bis-adduct, WCl4(Et2O)2, questions arose when elemental analyses were more in line with a mono-ether adduct, viz. WCl4(Et2O). It was proposed that this was due to the thermal instability of the bis-adduct. Here, we report the room-temperature X-ray crystal structure and Hirshfeld surface characteristics of trans-tetrachloridobis(diethyl ether)tungsten(IV), trans-WCl4(Et2O)2 or trans-[WCl4(C4H10O)2]. The compound crystallizes, with half of the molecule in the asymmetric unit, in the centrosymmetric space group P21/n. The W-O distance is 2.070 (2) Å, while the W-Cl distances are 2.3586 (10) and 2.3554 (10) Å.

Crystal structure and Hirshfeld surface analysis of the elusive trichlorobis(diethyl ether)oxomolybdenum(V).

First reported in 1930, MoCl3O(Et2O)2 is a by-product of the reductive synthesis of MoCl4(OEt2)2 from MoCl5. We report herein the X-ray crystal structure and Hirshfeld surface characteristics of mer-MoCl3O(Et2O)2, or [MoCl3O(C4H10O)2]. The compound crystallizes in the orthorhombic space group P212121. The molybdenyl (Mo=O) bond length is 1.694 (3) Šand the cis- and trans-Mo-O distances are 2.157 (3) and 2.304 (3) Å, respectively. Intermolecular Mo=O...H bonding is present in the lattice, with the shortest distance being 2.572 Å.

An Atomistic Understanding of the Unusual Thermal Behavior of the Molecular Oxide Tc2O7.

The thermal behavior of Tc2O7 has been investigated by single-crystal X-ray diffraction of the solid state over a range of 80-280 K and by ab initio molecular dynamics (MD) simulations. The thermal expansion coefficient of the solid was experimentally determined to be 189 × 10-6 Å3 K-1 at 280 K. The simulations accurately reproduce the experimentally determined crystal structures and thermal expansion within a few percent. The experimental melting point and vapor pressure for Tc2O7 are unusually high and low, respectively, in comparison to similar molecular solids. Through investigating the structure and the motion of the solid across a range of temperatures, we provide insights into the thermal behavior of Tc2O7.

Catalytic Applications of Vanadium: A Mechanistic Perspective.

The chemistry of vanadium has seen remarkable activity in the past 50 years. In the present review, reactions catalyzed by homogeneous and supported vanadium complexes from 2008 to 2018 are summarized and discussed. 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.

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

Dimeric and monomeric supported single-site Fe(ii) pre-catalysts on SiO2 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. Preliminary XAS experiments on the H2-activated samples suggest the active species are isolated Fe(ii) sites.

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 Re2L4F2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp-); 2, L = diphenyl formamidinate (dpf-)) were prepared from the solid-state melt reactions (SSMRs) between (NH4)2[Re2F8]·2H2O and HL. 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 [Re2(hpp)4F2]PF6 (3) was prepared from the one-electron oxidation of Re2(hpp)4F2 with [Cp2Fe]PF6. Compounds 1-3 are isostructural with the corresponding chloro derivatives. In solution, compound 1 undergoes two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re2(hpp)4F2 (1) is more easily oxidized than its chloro and bromo analogues.

Molecular and Electronic Structures of M2O7 (M = Mn, Tc, Re).

The molecular and electronic structures of the group 7 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 Re2O7 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 undercorrelation of the metal d conducting states. Homologue and compression studies show that Re2O7 adopts a polymeric structure because the Re-oxide tetrahedra are easily distorted by packing stresses to form additional three-center covalent bonds.

Ditechnetium Heptoxide Revisited: Solid-State, Gas-Phase, and Theoretical Studies.

Ditechnetium heptoxide was synthesized from the oxidation of TcO2 with O2 at 450 °C and characterized by single-crystal X-ray diffraction, electron-impact mass spectrometry (EI-MS), and theoretical methods. Refinement of the structure at 100 K indicates that Tc2O7 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, and V = 557.5(3) Å3]. The Tc2O7 molecule can be described as corner-sharing TcO4 tetrahedron [Tc---Tc = 3.698(1) Å and Tc-OBri-Tc = 180.0°]. The EI-MS spectrum of Tc2O7 consists of both mononuclear and dinuclear species. The main dinuclear species in the gas-phase are Tc2O7 (100%) and Tc2O5 (56%), while the main mononuclear species are TcO3 (33.9%) and TcO2 (42.8%). The difference in the relative intensities of the M2O5 (M = Tc, Re) fragments (1.7% for Re) indicates that these group 7 elements exhibit different gas-phase chemistry. The solid-state structure of Tc2O7 was investigated by density functional theory methods. The optimized structure of the Tc2O7 molecule is in good agreement with the experimental one. Simulations indicate that the more favorable geometry for the Tc2O7 molecule in the gas-phase is bent (Tc-OBri-Tc = 156.5°), while a linear geometry (Tc-OBri-Tc = 180.0°) is favored in the solid-state.

Molecular and Electronic Structure of Re2Br4(PMe3)4.

The dinuclear rhenium(II) complex Re2Br4(PMe3)4 was prepared from the reduction of [Re2Br8](2-) with (n-Bu4N)BH4 in the presence of PMe3 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 Re2Cl4(PMe3)4 (2.247(1) Å). The molecular and electronic structure of Re2X4(PMe3)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 Re2Cl4(PMe3)4. The electronic absorption spectrum of Re2Br4(PMe3)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. 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.

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

A simple method for the high-yield preparation of (NH4)2[Re2F8]·2H2O has been developed that involves the reaction of (n-Bu4N)2[Re2Cl8] with molten ammonium bifluoride (NH4HF2). Using this method, the new salt [NH4]2[Re2F8]·2H2O was prepared in ∼90% yield. The product was characterized in solution by ultraviolet-visible light (UV-vis) and (19)F nuclear magnetic resonance ((19)F 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 [Re2F8](2-) anion. The metal-metal bonding in the Re2(6+) unit was quantified in terms of effective bond order (EBO) and compared to that of its [Re2Cl8](2-) and [Re2Br8](2-) analogues.

Recent advances in technetium halide chemistry.

Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/ß-TcCl3, α/ß-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (ß-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, ß-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc(IV)) to d(5) (Tc(II)) is accompanied by the formation of metal-metal bonds in the coordination polyhedra. There is no metal-metal interaction in TcX4, a Tc═Tc double bond is present in α/ß-TcCl3, and a Tc≡Tc triple bond is present in α/ß-TcCl2. We investigated the thermal behavior of these binary halides in sealed tubes under vacuum at elevated temperature. Technetium tetrachloride decomposes stepwise to α-TcCl3 and ß-TcCl2 at 450 °C, while ß-TcCl3 converts to α-TcCl3 at 280 °C. The technetium dichlorides disproportionate to Tc metal and TcCl4 above ∼600 °C. At 450 °C in a sealed Pyrex tube, TcBr3 decomposes to Na{[Tc6Br12]2Br}, while TcI3 decomposes to Tc metal. We have used technetium tribromide in the preparation of new divalent complexes; we expect that the other halides will also serve as starting materials for the synthesis of new compounds (e.g., complexes with a Tc3(9+) core, divalent iodide complexes, binary carbides, nitrides, and phosphides, etc.). Technetium halides may also find applications in the nuclear fuel cycle; their thermal properties could be utilized in separation processes using halide volatility. In summary, we hope that these new insights on technetium binary halides will contribute to a better understanding of the chemistry of this fascinating element.

Magnetic circular dichroism and electronic structure of [Re2X4(PMe3)4]+ (X = Cl, Br).

Magnetic circular dichroism (MCD) and electronic absorption spectroscopies have been used to probe the electronic structure of the classical paramagnetic metal-metal-bonded complexes [Re2X4(PMe3)4](+) (X = Cl, Br). A violation of the MCD sum rule is observed that indicates the presence of ground-state contributions to the MCD intensity. The z-polarized δ → δ* band in the near-IR is formally forbidden in MCD but gains intensity through a combination of ground- and excited-state mechanisms to yield a positive C term.

Synthetic and coordination chemistry of the heavier trivalent technetium binary halides: uncovering technetium triiodide.

Technetium tribromide and triiodide were obtained from the reaction of the quadruply Tc-Tc-bonded dimer Tc2(O2CCH3)4Cl2 with flowing HX(g) (X = Br, I) at elevated temperatures. At 150 and 300 °C, the reaction with HBr(g) yields TcBr3 crystallizing with the TiI3 structure type. The analogous reactions with flowing HI(g) yield TcI3, the first technetium binary iodide to be reported. Powder X-ray diffraction (PXRD) measurements show the compound to be amorphous at 150 °C and semicrystalline at 300 °C. X-ray absorption fine structure spectroscopy indicates TcI3 to consist of face-sharing TcI6 octahedra. Reactions of technetium metal with elemental iodine in a sealed Pyrex ampules in the temperature range 250-400 °C were performed. At 250 °C, no reaction occurred, while the reaction at 400 °C yielded a product whose PXRD pattern matches the one of TcI3 obtained from the reaction of Tc2(O2CCH3)4Cl2 and flowing HI(g). The thermal stability of TcBr3 and TcI3 was investigated in Pyrex and/or quartz ampules at 450 °C under vacuum. Technetium tribromide decomposes to Na{[Tc6Br12]2Br} in a Pyrex ampule and to technetium metal in a quartz ampule; technetium triiodide decomposes to technetium metal in a Pyrex ampule.

ß-Technetium dichloride: solid-state modulated structure, electronic structure, and physical properties.

A second polymorph of technetium dichloride, ß-TcCl2, has been synthesized from the reaction of Tc metal and chlorine in a sealed tube at 450 °C. The crystallographic structure and physical properties of ß-TcCl2 have been investigated. The structure of ß-TcCl2 consists of infinite chains of face sharing [Tc2Cl8] units; within a chain, the Tc≡Tc vectors of two adjacent [Tc2Cl8] units are ordered in the long-range where perpendicular and/or parallel arrangement of Tc≡Tc vectors yields a modulated structure. Resistivity and Seebeck measurements performed on a ß-TcCl2 single crystal indicate the compound to be a p-type semiconductor while a magnetic susceptibility measurement shows technetium dichloride to be diamagnetic. A band gap of 0.12(2) eV was determined by reflectance spectroscopy measurements. Theoretical calculations at the density functional level were utilized for the investigation of other possible stable forms of TcCl2.

Recent developments in the synthetic chemistry of technetium disulfide.

Technetium disulfide was prepared by reaction between the elements in a sealed tube at 450 °C, by reaction between Tc2(O2CCH3)5 and H2S gas in a flowing system at 450 °C and by reaction between K2TcCl6 and H2S gas in sulfuric acid. The samples were analysed by X-ray absorption fine structure (XAFS) spectroscopy.