13637-68-8Relevant articles and documents
Synthesis and structure of lipophilic dioxo-molybdenum (VI) bis(hydroxamato) complexes
Dzyuba, Valeriy I.,Koval, Lyudmila I.,Bon, Vladimir V.,Pekhnyo, Vasyl I.
, p. 2900 - 2906 (2010)
New methods for the synthesis of complexes of molybdenyl with hydrophobic alkyl-substituted hydroxamic acids have been developed. A number of novel coordination compounds of the general formula MoO2L2 (where HL is decano-, N-methyl-decano-, N-methyl-hexano-, N-methyl-1-adamantano- and N-tert-butyl-hexanohydroxamic acids) have been synthesized. All compounds obtained have been characterized by IR, 1H NMR spectroscopy and X-ray crystallography. The effect of the electron donating and steric properties of ligand substituents on the structure of complexes is discussed.
ELECTROCHEMICAL REDUCTION OF MOLYBDENUM(VI) COMPOUNDS IN MOLTEN LITHIUM CHLORIDE-POTASSIUM CHLORIDE EUTECTIC.
Popov,Laitinen
, p. 1346 - 1350 (1973)
This investigation was undertaken in order to study the reduction of molybdenum(VI) compounds and to characterize any reduction products observed. It was also considered possible that some aspects of molybdenum chemistry and interactions between molybdenu
Determination of intrinsic kinetics parameters for MoO3 chlorination with Cl2 gas between 798 and 873 K
De Micco,Carignan,Canavesio,Bohé
, p. 211 - 217 (2012)
In this work the kinetics of the chlorination of molybdenum trioxide has been studied by thermogravimetry between 798 and 873 K. The starting temperature for the reaction of MoO3 with chlorine is determined at about 770 K. The influence of gaseous flow rate, sample mass, temperature, and chlorine partial pressure in the reaction rate is analyzed for two MoO3 samples having different particle size and morphology. The experimental conditions for chemical control of the reaction rate were established for both types of samples. An average activation energy of 211 kJ mol-1 and a reaction order of 1 with respect to chlorine partial pressure were determined for the chlorination of MoO3 with gaseous chlorine. A complete rate equation was formulated that describes the reaction evolution of each type of solid.
THE INFRARED SPECTRA OF THE MoCl, MoO2Cl2, WOCl, WO2Cl2, MoO2, MoO3 AND Mo3O9 GASEOUS MOLECULES
Neikirk, D. L.,Fagerli, J. C.,Smith, M. L.,Mosman, D.,Devore, T. C.
, p. 165 - 181 (1991)
The IR spectra of several gaseous molybdenum and tungsten oxides and oxychlorides which are thought to be transporting agents for these metals in halogen lamps have been obtained.MoO2Cl2 and WO2Cl2 were observed in absorption and emission by heating the solid compounds; Mo3O9 was observed in absorption by heating the solid and by observing the products of the reaction between Mo and N2O; MoO2 and MoO3 were observed as products from the reaction between Mo and N2O; and MoOCl and WOCl were formed from the reaction between the metal and POCl3.All spectra were obtained at a resolution of 0.5 cm-1 which permits the band shapes to be resolved and definite spectral assignments.
An Inelastic Electron-Tunneling Spectroscopic Investigation of the Reaction of Molybdenum Oxychlorides with a Hydroxylated Aluminum Oxide Surface
Gajda, G. J.,Grubbs, R. H.,Weinberg, W. H.
, p. 5627 - 5633 (1987)
Molybdenum oxytetrachloride adsorbs on alumina at 22 deg C and reacts with the surface hydroxyl groups to form a dimeric oxydichloride-molybdenum complex.This complex desorbs slowly from the surface, as molybdenum dioxodichloride.Heating the surface during oxytetrachloride exposure yields poorly characterized decomposition products and tunnel junctions with very large conductivity changes as a function of bias voltage.Molybdenum dioxodichloride adsorbs on alumina at 22 deg C and forms an oligomerized molybdenum trioxide species.This oxide adsorbs water at a background pressure of approximately 1E-7 Torr, and it can be dehydrated by heating under vacuum to 100 deg C.Heating the surface during the vapor-phase exposure of molybdenum dioxodichloride, or the molybdenum oxide under vacuum after the exposure, increases the extent of polymerization.Exposure of the oxide to 2 Torr of ethylene at 100 deg C or 1E-1 Torr of acetic acid at 22 deg C produces changes in the tunneling spectra, due to increased oligomerization and some decomposition of the adsorbates, but there is no evidence for molecular adsorption or hydrocarbon formation.Exposure of the oxide to 5E-2 Torr of 4-tert-butylpyridine at 22 deg C causes the complete desorption of the oxide, presumably as the tripyridine complex.
OXYHALIDE PRECURSORS
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Page/Page column 5-7, (2021/01/29)
The invention provides a process for preparing molybdenum and tungsten oxyhalide compounds which are useful in the deposition of molybdenum and tungsten containing films on various surfaces of microelectronic devices. In the process of the invention, a molybdenum or tungsten trioxide is heated in either a solid state medium or in a melt-phase reaction comprising a eutectic blend comprising alkaline and/or alkaline earth metal salts. The molybdenum or tungsten oxyhalides thus formed may be isolated as a vapor and crystallized to provide highly pure precursor compounds such as MoO2Cl2.
Molecular and Inner Complex Compounds of Dioxomolybdenum(VI) with Disubstituted Salicydenealcoholimines: Crystal Structure of 1 : 1 Dioxo(3,5-Dibromosalicylidenemonoethanoliminato)molybdenum(VI) Solvate with Methanol [MoO2(L1) · MeOH] (L1 = C9H7Br2NO2)
Sergienko,Abramenko,Gorbunova, Yu. E.,Churakov
, p. 876 - 882 (2020/01/13)
Abstract: Complexes of dioxomolybdenum(VI) of the molecular (МоО2Сl2 · 2H2L) and inner complex ([MoO2L · Solv]) types are synthesized (H2L are azomethines, derivatives of disubstituted R1,R2-salicylaldehydes (R1, R2 = 3.5-Вr2; R1 = 3-МеО, R2 = 5-Вr) and monoethanolamine; Solv is a methanol, dimethylformamide, pyridine, or α-picoline molecule). The cis-octahedral structure of the complexes is concluded on the basis of the IR spectroscopic data. In the molecular compounds, the ligands are coordinated via the O atom of the carbonyl group of the H2L tautomeric form. In the inner complex compounds, the ligands are coordinated in the deprotonated benzoid form. The structure of [MoO2(L1) · МеОН] (I) (where L1 is C9H7Br2NO2) is determined by X-ray diffraction analysis (СIF file CCDC no. 1898088). In the mononuclear molecule of compound I, the Mo atom has the octahedral coordination by two oxo ligands, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) two-charge ligand (L1)2–, and the O atom of the methanol molecule. The neutral N(1) and O(1) atoms of the L1 and МеОН ligands, respectively, are arranged in the trans positions to the O(oxo) ligands. The Mo–N(1) (2.265 ?) and Мо–О(1) (2.372 ?) bonds are substantially elongated due to the structural manifestation of the trans effect of the multiply bonded oxo ligands. The intermolecular hydrogen bonds (МеОН)О–Н···О(oxo) join the molecules into supramolecular 1D chains.
Spectroscopic Studies on Matrix-isolated Molybdenum Pentachloride
Brisdon, Alan K.,Graham, John T.,Hope, Eric G.,Jenkins, Delyth M.,Levason, William,Ogden, J. Steven
, p. 1529 - 1532 (2007/10/02)
Matrix-isolation studies have been carried out on molybdenum petnachloride.In a nitrogen-matrix, prominent i.r. bands are observed at ca. 473 and 408 cm-1, which on the basis of isotope studies are assigned as the A1 (axial and E Mo-Cl stretching modes of monomeric MoCl5 (C4v).Argon matrices yielded essentially the same spectroscopic features.Corresponding u.v.-visible spectra were obtained and assigned on the basis of a square-pyramidal geometry.Attempts to prepare and characterise MoCl6 were unsuccessful.
Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins
Schrock, Richard R.,Murdzek, John S.,Bazan, Gui C.,Robbins, Jennifer,DiMare, Marcello,O'Regan, Marie
, p. 3875 - 3886 (2007/10/02)
The reaction between Mo(C-t-Bu)(dme)Cl3 (dme = 1,2-dimethoxyethane) and Me3SiNHAr (Ar = 2,6-diisopropylphenyl) yields Mo(C-t-Bu)(NHAr)Cl2(dme) (1), which upon treatment with a catalytic amount Of NEt3 is transformed into Mo(CH-t-Bu)(NAr)Cl2(dme) (2). Complexes of the type Mo(CH-t-Bu)(NAr)(OR)2 (OR = OCMe(CF3)2, OCMe2(CF3), O-t-Bu, or OAr) have been prepared from 2. Complexes of the type Mo(C-t-Bu)(NHAr)(OR)2 (OR = OCMe(CF3)2 or OAr) have been prepared from 1, but they cannot be transformed into Mo(CH-t-Bu)(NAr)(OR)2 complexes. A precursor to imido alkylidene complexes that is related to 2 has been prepared by the sequence MoO2 → MoO2Cl2 → Mo(NAr)2Cl2 → Mo-(NAr)2(CH2R′)2 → Mo(CHR′)(NAr)(OTf)2(dme) (R′ = t-Bu or CMe2Ph; OTf = OSO2CF3). Mo(CH-t-Bu)(NAr)(OTf)2(dme) crystallizes in the space group P1 with a = 17.543 ?, b = 19.008 ?, c = 9.711 ?, α = 91.91°, β = 99.30°, γ = 87.27°, Z = 4, Mr = 729.60, V = 3191.1 ?3, ρ(calcd) = 1.518 g cm-3. It is a pseudooctahedral species in which the imido and alkylidene ligands are cis to one another, the triflate ligands are mutually trans, and the tert-butyl group points toward the imido ligand (syn orientation). Neophylidene complexes, Mo(CHCMe2Ph)(NAr)(OR)2 (OR = O-t-Bu, OAr, or O-2-C6H4-t-Bu), have been prepared from Mo(CHCMe2Ph)(NAr)(triflate)2(dme). Activity for the metathesis of cis-2-pentene by Mo(CHR′)-(NAr)(OR)2 complexes roughly correlates with the electron-withdrawing ability of OR, being rapid when OR = OCMe(CF3)2 and slow to negligible when OR = O-t-Bu. In several cases it is clear from proton NMR studies that the alkylidene ligand can rotate on the NMR time scale; in Mo(CHSiMe3)(NAr)(OAr)2 it has been shown that ΔG?298 = 16.0 kcal mol-1 for this process. Mo[CH(SiMe3)CH(SiMe3)CH2](NAr)[OCMe 2(CF3)]2 has been observed and found to be ～3 orders of magnitude less stable than the analogous tungsten complex. Trigonal-bipyramidal Mo(CH2CH2CH2)(NAr)[OCMe(CF3) 2]2 can be prepared at 25 °C in high yield, but it decomposes over a period of 12 h. Instability of OCMe(CF3)2 metallacyclobutane complexes has been traced to reduction by β-hydride rearrangement to give an olefin. In one case a complex containing the olefin product, Mo(NAr)(Me3SiCH=CH2)[OCMe(CF3)2] 2, was isolated.
The Crystal Structure of Nonachlorodimolybdenum(V) Heptachlorodioxo-dimolybdate(V)
Edwards, Anthony J.,Slim, David R.
, p. 485 - 488 (2007/10/02)
The compound Mo2Cl8O was formed as a minor product in the reaction of molybdic acid with thionyl chloride.Its structure has been determined by the heavy-atom method from 1265 reflections, measured with a diffractometer, and refined by full-matrix least-squares methods to R 0.066.Crystals are monoclinic, space group P2/c, with a=10.01(1), b=6.27(1), c=17.89(2) Angstroem, β=101.8(3) grad.The structure consists of singly chlorine-bridged, binuclear cations + and triply chlorine-bridged binuclear anions - which are linked into chains by weak interactions through the oxygen atoms.
