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Book ChapterDOI

The Organometallic and Metal-Organic Chemistry of Molybdenum

01 Jan 1994-Studies in Inorganic Chemistry (Elsevier)-Vol. 19, Iss: 42, pp 277-402
About: This article is published in Studies in Inorganic Chemistry.The article was published on 1994-01-01. It has received 3 citations till now. The article focuses on the topics: Molybdenum.
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Reference EntryDOI
21 May 2020
TL;DR: In this article, the authors present a survey of the Molybdenum chemistry and its application in various areas of industry, such as mining, automotive, agriculture, and economic aspects.
Abstract: The article contains sections titled: 1. Introduction 2. Properties 3. Occurrence 3.1. Minerals 3.2. Deposits 4. Production 4.1. Concentration 4.2. Processing of Concentrate 4.3. Recovery from Spent Petroleum Catalysts 4.4. Recovery during Production of Tungsten Ores 4.5. Production of Molybdenum Metal Powder 4.6. Production of Compact Molybdenum Metal 4.7. Processing of Molybdenum 4.8. Molybdenum-Base Alloys 5. Uses 6. Production of Ferromolybdenum 6.1. Ferromolybdenum Grades 6.2. Raw Materials 6.3. Submerged Arc Furnace Carbothermic Reduction 6.4. Metallothermic Reduction 7. Molybdenum Compounds 7.1. Overview of Molybdenum Chemistry 7.2. Molybdenum Oxides 7.3. Molybdenum Chalcogenides 7.4. Molybdenum Halides 7.5. Molybdates, Isopolymolybdates, and Heteropolymolybdates 7.6. Other Molybdenum Compounds 8. Uses of Molybdenum Compounds 8.1. Catalysis 8.2. Lubrication 8.3. Corrosion Inhibition 8.4. Flame Retardancy and Smoke Suppression 8.5. Pigments 8.6. Agriculture 9. Analysis 10. Economic Aspects 11. Environmental Aspects 12. Toxicology and Occupational Health

35 citations

Journal ArticleDOI
TL;DR: The heteroleptic molybdenum complexes have been analyzed quantitatively by means of linear solvation energy relationships based on Kamlet-Taft solvatochromism parameters, as well as on Drago's "unified scale of solvent polarity".
Abstract: The heteroleptic molybdenum complexes [{Mo(NO)Tp*X}n(L-L)] [Tp* = HB(3,5-Me2C3HN2)3; X = Cl, I; L-L = 4-NC5H4(CHCH)4C5H4N-4‘, n = 1, 2; X = Cl; L-L = {4,4‘-NC5H4CHCHC(Me)CHCH=}2, n = 2] have a low energy absorbance in their electronic spectra which exhibits solvatochromic shifts. These have been analyzed quantitatively by means of linear solvation energy relationships based on Kamlet−Taft solvatochromism parameters, as well as on Drago's “unified scale of solvent polarity”. Each of these approaches leads to satisfactory linear models, in qualitative agreement with one another. The solvatochromism is due to a combination of increased solvent dipolarity/polarizability and solvent-to-solute hydrogen bonding, each preferentially stabilizing polar ground states compared with less polar excited states. The latter originate from metal-to-ligand charge transfer. Quantitatively, the Drago and Kamlet−Taft models differ somewhat. The former are statistically slightly better than those based on Kamlet−Taft parameters.

15 citations

Journal Article
TL;DR: In this paper, the reaction between [WBr 3 (CO) 2 (η 5 -C 5 H 5 )] and excess of Tl(SC 6 F 5 ) affords Tl[WBr 2 (CO), η 5 −C 5H 5 )] (2b) as the major product and [W(SC6F 5 ) 3 ( CO), Δ − 5 − C 5 H5 )] (3) as minor product.
Abstract: The reaction between [WBr 3 (CO) 2 (η 5 -C 5 H 5 )] and excess of Tl(SC 6 F 5 ) affords Tl[W(SC 6 F 5 ) 4 (η 5 -C 5 H 5 )] (2b) as the major product and [W(SC 6 F 5 ) 3 (CO)(η 5 -C 5 H 5 )] (3) as the minor product. Complex (3) has been structurally characterised as its 0.5 CH 2 Cl 2 solvate by X-ray diffraction
References
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Journal ArticleDOI
TL;DR: In this paper, a new class of 12-electron tetranuclear alkoxide clusters, IV-XI, for both molybdenum and tungsten were characterized.
Abstract: The authors are interested in developing efficient synthetic routes to alkoxide-supported molybdenum and tungsten clusters that may prove to be excellent models for fragments of reduced oxides of the same metals. These clusters should include both coordinative unsaturation and redox flexibility at the metal centers to initiate organometallic chemistry upon substrate reduction. Complementary metal oxide model systems such as polyoxoanions may prove effective for oxidation catalysis. They have recently demonstrated that W/sub 2/(O-i-Pr)/sub 6/ (I) exists in reversible equilibrium with its 12-electron cluster W/sub 4/(O-i-Pr)/sub 12/ (II) in solution at room temperature, eq 1, whereas Mo/sub 2/(O-i-Pr)/sub 6/ is indefinitely stable with respect to cluster formation. Even by reducing the steric demands at the molybdenum center they were unable to induce the formation of new metal-metal bonds in (Mo/sub 2/(O-i-Pr)/sub 5/(OMe))/sub 2/ (III), which instead retains isolated, unbridged Mo-Mo triple bonds. The authors report here the isolation and characterization of members of a new class of 12-electron tetranuclear alkoxide clusters, IV-XI, which are spectroscopically isostructural for both molybdenum and tungsten together with the single-crystal X-ray diffraction structure of one derivative, (Mo/sub 4/(O-CH/sub 2/-c-Bu)/sub 12/(HO-CH/sub 2/-c-Bu)) (XI) (where c-Bu = cyclobutyl). This represents the first group of structurally related homoleptic alkoxidemore » clusters for molybdenum and tungsten in oxidation state (3+).« less

25 citations

Journal ArticleDOI
TL;DR: In this paper, the reaction of Mo2(CO)4(µ-R1C2R2)(η-C5H5)2] with PPh2Cl proceeds via P-Cl bond cleavage and coupling of the diphenylphosphido group with the alkyne in one of three different ways depending on the nature of R1 and R2.
Abstract: The reaction of [Mo2(CO)4(µ-R1C2R2)(η-C5H5)2](R1,R2= H, alkyl, or aryl) with PPh2Cl proceeds via P–Cl bond cleavage and coupling of the diphenylphosphido group with the alkyne in one of three different ways depending on the nature of R1 and R2; two of the resulting complexes, [Mo2(µ-Cl){µ-Ph2PC(H)CH}(CO)2(η-C5H5)2] and [Mo2Cl2(µ-PPh2PCCHMe)(η-C5H5)2] have been characterised by X-ray analysis.

25 citations

Journal ArticleDOI
TL;DR: In this paper, a trans-Cr(CO) 4 PPh 3 L] + +PPh 3 (PPh3 L) is defined, and the coordinat L: trans[Cr(Co) 4 pPh 3 ) 2 ] + +L→trans[Cr[Co] 4 pph 3 L ] +L] +L

25 citations

Journal ArticleDOI
TL;DR: In this article, Li2M(NBut)4(M = Mo or W) have been made by deprotonation of M(Nbut)2(NHBut)2 in diethyl ether by methyl-lithium.
Abstract: The compounds Li2M(NBut)4(M = Mo or W) have been made by deprotonation of M(NBut)2(NHBut)2 in diethyl ether by methyl-lithium. Interaction of Li2M(NBut)4 with AlCl3, GaCl3, and AlMe3 gives rise to compounds of the type M[(µ-NBut)2M′X2]2 and the crystal structures of compounds where M = W, M′= Al, X = Cl and Me have been determined. The Li2M(NBut)4 compounds are readily protonated by weak acids such as water or MeOH. Interaction with strong acids gives initially M(NBut)2(NHBut)2 and further protonation of the amido compound by CF3SO3H or CF3CO2H gives octahedral neutral species such as M(NBut)2(NH2But)2(OSO2CF3)2; W(NBut)2(NHBut)2 with HBF4 gives only monoprotonation forming two species, [W(NBut)2(NHBut)(NH2But)]BF4 and W(NBut)2(NHBut)(NH2But)(F2BF2), depending on the conditions; HCl gives [W(NBut)2(NH2But)Cl(µ-Cl)]2. Interaction of Li2W(NBut)4 with [Cu(MeCN)4]BF4 gives a remarkable cation of stoicheiometry [WVI2CuI5(NBut)2(µ-NBut)6(NHBut)2]+ in which each W has one linear terminal NBut group and three NBut groups bridging to three copper(I) atoms in a triangle; two of these NBut groups are also bound to a CuI(NHBut) unit thus being µ3.

25 citations