Two mononuclear molybdenum(VI) oxo complexes with tridentate hydrazone ligands: Synthesis,structures, and thermal stability

A reaction of [MoO₂(acac)₂] (where acac = acetylacetonate) with two hydrazone ligands in methanol yields two mononuclear molybdenum(VI) oxo complexes with the general formula [MoO₂L(CH₃OH)], where L = L¹=(4-nitrophenoxy)acetic acid [1-(5-chloro-2-hydroxyphenyl)methylidene]hydrazide (H₂L¹) and L = L²=4-dimethylaminobenzoic acid [1-(2-hydroxy-3-methoxyphenyl)methylidene]hydrazide (H₂L²). The crystal and molecular structures of the complexes are determined by the single crystal X-ray diffraction method. All of the investigated compounds are further characterized by the elemental analysis, FT-IR spectra, and thermogravimetric analysies. Single crystal X-ray structural studies indicate that hydrazone ligands coordinate to MoO₂ cores through enolate oxygen, phenolate oxygen, and azomethine nitrogen atoms. The Mo atoms in both complexes are in octahedral coordination.     

Mo2O3Cl4(Pyridin)4 · CH2Cl2 Synthese,IR-Spektrum und Kristallstruktur

Mo₂O₃Cl₄(Pyridine)₄ · CH₂Cl₂. Synthesis, IR Spectrum, and Crystal Structure Reduction of MoO₂Cl₂(pyridine)₂ with triphenylphosphane in toluene and recrystallisation from CH₂Cl₂ yields brown crystal needles of the complex Mo₂O₃Cl₄(pyridine)₄ · CH₂Cl₂. The compound crystallizes monoclinic in the space group P2₁/c with four formula units per unit cell of the dimensions a = 1 234.6 pm; b = 1 593 pm, c = 1 522.3 pm and β = 105.66° A structural investigation by X-ray methods (3 276 independent observed reflexions, R = 0.033) reveals the molecule with two molybdenum atoms in a distorted octahedral coordination linked by an almost linear Mo? O? Mo bridge with bond distances of 167 and 168 pm, respectively. The chlorine atoms are located in trans-position to the oxygen atoms which have different trans effects: The Mo? Cl bond opposite the bridge (length 242 pm) is 8 pm shorter than the bond in trans position to the terminal oxo ligands. The pyridine nitrogen atoms are in trans position to each other and complete the coordination of the molybdenum atoms. The i.r. spectrum of the compound is reported.     

Cyclooctene epoxidation with H2O2 and single crystal X-ray determined crystal structures of new molybdenum and tungsten catalysts bearing the hydrophilic ligand hydroxymethyldiphenylphosphine oxide

The dioxo molybdenum and tungsten complexes MoO₂Cl₂(OPPh₂CH₂OH)₂ and WO₂Cl₂(OPPh₂CH₂OH)₂ have been synthesized and characterized by FT-IR, ¹H and ³¹P NMR. Their structures, as determined by single crystal X-ray diffraction analysis, reveal distorted octahedral geometries with cis terminal oxygen atoms, trans Cl ligands and that the hydroxymethyldiphenylphosphine oxide ligands coordinate through the oxygen atom bonded to the P atom. Both of the compounds are studied as catalysts for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as a source of oxygen. Both complexes showed good activity and very high selectivity for the formation of cyclooctene oxide.     

Complex [MoO2(L)(CH3OH)] (L2- = 3-methoxysalicylidenemonoethanolimine anion): Synthesis,crystal and molecular structures

The complex [MoO₂(L)(CH₃OH)] (where L^2- is 3-methoxysalicylidenemonoethanolimine anion) has been prepared and structurally characterized by X-ray diffraction. The molybdenum atom has an octahedral coordination to two ligands in cis-positions to each other, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) L^2- ligand, and also the oxygen atom of methanol. Strong O-H?O hydrogen bonds (O?O, 2.598 Å) link pairs of molecules into centrosymmetric pseudo-dimers.     

Two mononuclear molybdenum(VI) oxo complexes with tridentate hydrazone ligands: Synthesis and crystal structures

Reaction of [MoO₂(Acac)₂] (Acac = acetylacetonate) with two similar hydrazone ligands in methanol yielded two mononuclear molybdenum(VI) oxocomplexes with general formula [MoO₂(L)(CH₃OH)], where L = L¹ = (4-nitrophenoxy)acetic acid [1-(3-ethoxy-2-hydroxyphenyl)methylidene]hydrazide (H₂L¹) and L = L² = (4-nitrophenoxy)acetic acid [1-(5-bromo-2-hydroxyphenyl)methylidene]hydrazide (H₂L²). Crystal and molecular structures of the complexes were determined by single crystal X-ray diffraction method. All investigated compounds were further characterized by elemental analysis and FT-IR spectra. Single crystal X-ray structural studies indicate that the hydrazone ligands coordinate to the MoO₂ cores through enolate oxygen, phenolate oxygen, and azomethine nitrogen. The Mo atoms in both complexes are in octahedral coordination.     

The Monomerization of a Binuclear Molybdenum(VI) Dioxo Complex by an Unusual Silylation Reaction

The formation of a mononuclear molybdenum(VI) complex [MoO₂{O(CH₂)₂S(CH₂)₂OH}(OSiBu^tPh₂)] ( 2 ) derived from its binuclear precursor [MoO₂{O(CH₂)₂S(CH₂)₂O}]₂ ( 1 ) by a silylation reaction accompanied by the conversion of methanol to chloromethane is reported.     

Synthesis,crystal structures,and catalytic property of dioxomolybdenum(VI) complexes with hydrazones

Two new dioxomolybdenum(VI) complexes, [MoO₂(L₁)] _n · 0.5 _n CH₃OH (I) and [MoO₂(L₂)(CH₃OH)] (II), where L1 and L₂ are the dianionic form of N′-[1-(4-diethylamino-2-hydroxyphenyl)methylidene]isonicotinohydrazide and N′-(2-hydroxy-4-methoxybenzylidene)-3-methylbenzohydrazide, respectively, were prepared and structurally characterized by physicochemical and spectroscopic methods and single-crystal X-ray determination. For complex I, a polymeric structure is obtained, which is linked by coordination of the pyridine N atoms to the Mo atoms of other [MoO₂(L₁)] units. Complex II is a mononuclear molybdenum compound. In both complexes, the Mo atoms are in octahedral coordination. The catalytic properties of the complexes indicate that they are efficient catalysts for sulfoxidation.     

X-ray Photoelectron Spectroscopy and Time-Of-Flight Secondary Ion Mass Spectroscopy studies of electrodeposited molybdenum oxysulfide cathodes for lithium and lithium-ion microbatteries

Thin-film molybdenum oxysulfide cathodes for lithium and lithium–ion microbatteries were fabricated by a simple electrodeposition method. According to Scanning Electron Microscopy (SEM) data, the deposition parameters affect the morphology of the cathodes. X-ray diffraction (XRD) tests indicated that the sub-micron-thick molybdenum oxysulfide films are amorphous or form too small crystallites to give rise to detectable X-ray diffraction peaks. A variety of poly-ion clusters containing both oxygen and sulfur (like MoOS, MoO₂S and MoS₂O and others) detected by TOF-SIMS tests unambiguously indicates the formation of molybdenum oxysulfide compounds, and not a mixture of oxides and sulfides, during electrodeposition. The sulfur-to-oxygen ratio in the bulk of the deposit is about 1.76 and does not depend much on the electrodeposition parameters. XPS studies reveal that electrodeposition in unbuffered solutions produces deposits with high oxygen and low sulfur content, as compared with cathodes deposited in buffered solutions. Potentiostatic, as compared to galvanostatic deposition, is followed by the formation of cathode films with slightly higher sulfur and lower oxygen content at the same pH. An increase in the pH of electrolyte solutions from 8 to 9.5 slightly reduces sulfur content, but appreciably increases oxygen concentration. Charge–discharge overpotential of Li/hybrid polymer electrolyte microbatteries is lower in sulfur-rich MoO_xS_y cathodes.     

The initial oxidation of polycrystalline thorium

The initial oxidation of clean, polycrystalline α‐Th from background CO/CO₂ and saturation of the Th surface by O₂ has been examined by angle‐resolved Auger electron spectroscopy (ARAES) and time of flight secondary ion mass spectrometry (ToF‐SIMS). Following dissociative adsorption of very low doses of background CO/CO₂ (<1 L), the carbon surface population was dominant and spontaneously formed thorium carbide. The accompanying oxygen population increased at a rate roughly one‐third that of the carbon, suggesting simultaneous oxygen incorporation into the bulk. To further corroborate the surface kinetics of adsorbed oxygen, O₂ was admitted, following heating and sputter cleaning of the Th; some oxygen atoms continued to diffuse into the bulk until formation of stoichiometric ThO₂ at ～37 L. ARAES measurements showed an oxygen concentration gradient in the near‐surface region confirming rapid oxygen incorporation at low doses; however, once the surface is saturated, virtually no variation in the oxygen intensity is observed. AES and ToF‐SIMS depth profiling revealed complete oxide formation to a depth of 2 nm. Copyright © 2010 John Wiley & Sons, Ltd.     

Growth of carbon nanotubes from butadiene on a Fe-Mo-Al2O3 catalyst

The MoO₃-Fe₂O₃-Al₂O₃ catalysts were prepared from metal nitrates using a coprecipitation method. It was found that the modification of an alumina-iron catalyst with molybdenum oxide resulted in the formation of a solid solution based on hematite, in which a portion of iron ions was replaced by aluminum and molybdenum ions. The MoO₃-Fe₂O₃-Al₂O₃ catalyst was reduced with a reaction mixture at 700°C. Under the action of 1,3-butadiene diluted with hydrogen, the solid solution based on hematite was initially converted into magnetite and then into an Fe-Mo alloy. The modification of an alumina-iron catalyst with molybdenum oxide considerably changed its properties in the course of carbon nanotube formation. As the Mo content was increased, the yield of carbon nanotubes passed through a maximum. The optimum catalyst was 6.5% MoO₃–55% Fe₂O₃-Al₂O₃. The addition of small amounts of MoO₃ (to 6.5 wt %) to the aluminairon catalyst increased the dispersity and modified the properties of active metal particles: because of the formation of an Fe-Mo alloy, the rate of growth decreased but the stability of carbon nanotube growth and the yield of the nanotubes increased. A further increase in the molybdenum content decreased the yield because molybdenum is inactive in the test process.     

Kristallstruktur des Molybdändioxiddichlorid-Phosphoroxidtrichlorid-Addukts MoO2Cl2 · POCl3

Crystal Structure of the Molybdenum Dioxide Dichloride — Phosphorus Oxide Trichloride Adduct MoO₂Cl₂ · POCl₃ The crystal structure of MoO₂Cl₂ · POCl₃ was determined by X-ray methods (R = 0.046; 2497 independent reflexions). MoO₂Cl₂ · POCl₃ crystallizes monoclinic in the space group P2₁/c with Z = 8. It forms nearly linear chains in which the Mo atoms are linked together via weakly bent and asymmetric oxo bridges (Mo? O = 172 and 218 pm). The Mo atoms are surrounded in a distorted octahedral coordination by one O and two Cl atoms (Mo? Cl = 230–232 pm) as terminal ligands and by the POCl₃ molecule and the bridging O atoms as well. The POCl₃ molecule (Mo? O = 233 pm) is located in trans position to the terminal oxo ligand (Mo? O = 166 pm).     

Hierarchically structured MoO2/dopamine-derived carbon spheres as intercalation electrodes for lithium-ion batteries

A hydrogen peroxide initiated sol-gel process involving molybdenum transformation in the presence of dopamine (Dopa) hydrochloride excess produced the metastable precipitate composed of polydopamine (PDopa) spheres coated with Dopa preintercalated molybdenum oxide, (Dopa)_xMoO_y@PDopa. The hydrothermal treatment (HT) of the (Dopa)_xMoO_y@PDopa precursor resulted in the simultaneous carbonization of Dopa and molybdenum reduction generating MoO₂ nanoplatelets distributed and confined on the surface of the Dopa-derived carbon matrix (HT-MoO₂/C). The consecutive annealing (An) of the HT-MoO₂/C sample at 600 °C under Ar atmosphere led to the formation of MoO₂ with increased Mo oxidation state and improved structural stability (AnHT-MoO₂/C). Annealing had also further facilitated interaction between the molybdenum-derived and Dopa-derived components resulting in the modification of the carbon matrix confirmed by Raman spectroscopy. Morphology of both materials is best described as Dopa-derived carbon spheres decorated with MoO₂ nanoplatelets. These integrated metal oxide and carbon structures were tested as electrodes for lithium-ion batteries in the potential window that corresponds to the intercalation mechanism of charge storage. The AnHT-MoO₂/C electrode showed enhanced electrochemical activity, with an initial specific discharge capacity of 260 mAh/g and capacity retention of 67% after 50 cycles, compared to the HT-MoO₂/C electrode which exhibited an initial specific discharge capacity of 235 mAh g^?1 and capacity retention of 47% after 50 cycles. The rate capability experiments revealed that the capacity of 93 mAh/g and 120 mAh/g was delivered by the HT-MoO₂/C and AnHT-MoO₂/C electrodes, respectively, when the current density was increased to 100 mA/g. The improved specific capacity, electrochemical stability, and rate capability achieved after annealing were attributed to higher crystallinity of MoO₂, increased oxidation state of Mo, and formation of the tighter MoO₂/carbon contact accompanied by the annealing assisted interaction between MoO₂ and Dopa-derived carbon.     

The crystal structure of a Di(tetramethylammonium)-bis[R,R-tartrato(2-)]-cis-dioxomolybdate(VI), (NMe4)2[MoO2(C4H4O6)2] · EtOH · 1.5 H2O,with comments on tartrate coordination

Summary In the salt (NMe₄[MoO₂(H₂tart)₂] · EtOH · 1.5 H₂O (H₄tart = R,R-(+)-tartaric acid) the tartrato-ligands are linked to molybdenum through a carboxyl oxygen and the vicinal deprotonated hydroxyl oxygen atom, with carboxyl oxygentrans to terminal oxygen of the MoO₂ cis-dioxo core. The configuration about Mo is A. The C-C-C-C torsion angles of the ligands are almost 180°. This enables inter-ligand H-bonding from the uncoordinated hydroxyl groups. The five skeletal atoms from the uncoordinated section of a ligand are nearly co-planar. The probable strong preference fortrans coordination of carboxyl must limit the range of dissolved molybdenum(VI)-tartrate species.     

Crystal structures of some crystal hydrates of binary molybdates

The structures of a series of binary molybdates with the lithium cation LiM(MoO₄) · H₂O (M = K⁺, Na⁺, Rb⁺, NH ₄ ⁺ ) are analyzed and compared. Except for LiNa(MoO₄) · 2H₂O, in all other compounds the lithium cations have a tetrahedral coordination formed by the oxygen atoms of the water molecules and molybdate groups. The structure of LiNa(MoO₄) · 2H₂O was found to contain a unique coordination polyhedron of lithium, i.e., a trigonal bipyramid formed by the O atoms of the water molecules and oxo anions.     

Crystal structure of two polymorphs of molybdenyl salicylidene-2-furfuriliminate (HL<Superscript>1</Superscript>) [MoO<Subscript>2</Subscript>(L<Superscript>1</Superscript>)<Subscript>2</Subscript>]

The crystal structures of two polymorphs of molybdenyl salicylidene-2-furfuryliminate [MoO₂(L¹)₂] have been solved by X-ray diffraction. Both complexes crystallize in centrosymmetric and non-centrosymmetric space groups (P2₁/c and Р2₁, respectively) of monoclinic system and have similar structures and close geometric parameters. The Мо atoms have a distorted octahedral coordination to two terminal oxo ligands in cis-positions to each other and two pairs of the oxygen atoms (cis- to О(oxo)) and the nitrogen atoms (trans- to О(oxo)) of two bidentate chelate ligands (L¹)^–.     

Synthesis, crystal, and molecular structure of the solvated complex [MoO2(L)] · DMF (L2− = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol anion)

A new dioxomolybdenum(VI) complex, [MoO₂(L)] · DMF, where L^2? = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol, has been synthesized. Its structure has been determined by X-ray diffraction analysis. The Mo atom is octahedrally coordinated by two oxo ligands that are in cis-positions with respect to each other, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) ligand L, and the DMF oxygen atom.     

The difference one ligand atom makes – An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur

The influence of sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (⁻O(CH₂)₃S(CH₂)₃O⁻) has been determined using EXAFS spectroscopy to be able to compare a feature of its solution structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh₃ to OPPh₃ with DMSO as oxygen donor with variation of both substrate concentrations.     

The unexpected decarbonylation of a molybdenum(O) dithiocarbamate and the formation of a molybdenum(V) dimeric product: Crystal structure of di-μ-sulfido-bis[oxo(pyrrolidinedithiocarbamato)molybdenum(V)]

The interaction of molybdenum hexacarbonyl with ammonium pyrrolidinedithiocarbamate in warm dimethylsulfoxide solution gives not the expected complex [NH₄][Mo(CO)₄(S₂CN(CH₂)₄)] but the molybdenum(V) dimer, di-μ-sulfido-bis[oxo(pyrrolidinedithiocarbamato)molybdenum(V)]. The structure of this oxidized product [MoO(S₂CN(CH₂)₄)S]₂ (1) was determined by single-crystal X-ray diffraction analysis. The crystals are triclinic, space group P$\text{I}$ with two molecules in a unit cell of dimensions a = 8.775(1), b = 16.592(2), c = 6.661(1) Å, α = 97.67(1), β = 97.89, γ = 80.23(1)°. The structure was solved by the heavy-atom method and refined by block-diagonal least-squares calculations to R = 0.037 for 3772 observed data. In the binuclear complex the two Mo atoms are bridged via two S atoms [Mo-S 2.303-2.317(1) Å]. Each Mo atom is also coordinated by a terminal O atom [1.688(4) and 1.682(4) Å] and two S atoms from the bidentate ligand [Mo-S 2.455-2.475(1) Å]. The geometry around the metal atoms is distorted square pyramidal.     

A FTIR assessment of surface acidity and dispersion of surface species in titania and alumina-supported molybdena

Adsorption of pyridine on the MoO₃/TiO₂ and MoO₃/Al₂O₃ systems has been studied by FTIR spectroscopy, in order to identify surface acid sites existing in samples with different molybdena loadings. The results show that both Lewis and Brönsted surface acid sites exist, whatever the molybdena loading. The percentage of Brönsted sites is larger for loadings below the theoretical monolayer, and should correspond to bidimensional molybdenum oxides species, while for loadings above the monolayer these sites are associated with bulk MoO₃.     

Rational Synthesis of Molybdenum(V) Tetramers Consisting of [Mo2O4]2+ Dimers Held Together by Bridging Phosphinate Ligands and the Tungsten(VI) Dimer [(CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2]: Structural and Theoretical Considerations

Reacting MoO₂(acac)₂ with Ph₂POOH or Me₂POOH in EtOH results in the formation of the tetranuclear molybdenum (V) clusters Mo₄(μ ₃-O)₄(μ-O₂PR₂)₄O₄, PR₂ = PPh₂, 1, or PMe₂, 2, in functional yields (>90% and 55% respectively). The reaction of WO₂(acac)₂ with Ph₂POOH in MeOH affords the tungsten dimer [(CH₃O)₂(O)W(μ-O)(μ-O₂PPh₂)₂W(O)(CH₃O)₂], 3. The single crystal X-ray determined structures of complexes 1–3 are reported. In 1 and 2, the four Mo=O units are interconnected by four triply bridging oxygen atoms, resulting in a distorted cubic-like structure for the Mo₄(μ ₃-O)₄O₄ units. Each molybdenum atom forms two additional Mo–O bonds with two oxygen atoms from different adjacent phosphinato ligands. Complex 3, a tungsten dimer, contains packing disorder and consists of bridging oxo and diphenylphosphinato ligands. The bonding of 1 and 2 assessed by density-functional methods showed that bonding between the Mo(V) centers occurs through σ overlap of the d _xy orbitals. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. Dedicated to the memory of Professor F. A. Cotton. Veritas numquam perit.