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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: The compound (t-BuO)/sub 3/Mo identical with N is formed in the reaction between Cl/sub 3 3/M identical with n and LiO-t 3/Bu (3 equiv) in THF and is obtained as a white crystalline compound by either sublimation or recrystallization from toluene.
Abstract: The compound (t-BuO)/sub 3/Mo identical with N is formed in the reaction between Cl/sub 3/Mo identical with N and LiO-t-Bu (3 equiv) in THF and is obtained as a white crystalline compound by either sublimation (85/sup 0/C, 5 x 10/sup -3/ torr) or recrystallization from toluene. In the solid state the compound forms a linear polymer ((t-BuO)/sub 3/Mo identical with N) involving alternating short, 1.66 (1) A, and long, 2.86 (2) A, Mo-N bonds, corresponding formally to triple and weak dative bonds, respectively. In benzene solution, a cryoscopic molecular weight determination indicates the monomeric species is present. The solubilities of the compounds ((t-BuO)/sub 3/M identical with N) where M = Mo and W differ quite markedly, with the molybdenum compound being appreciably more soluble in aromatic solvents. It is suggested that this results from different M identical with N - M bonding along the infinite chain with the tungsten compound having a more basic or nucleophilic nitrogen atom. This suggestion finds support from MO calculations employing the Fenske-Hall method. The W identical with N distance is significantly longer (1.740 (15) A) and the W-N distance shorter (2.661 (15) A). Furthermore, the molybdenum and tungsten compounds differ in their reactivity towardmore » alcohols, yielding, respectively, (RO)/sub 3/Mo identical with N and W(OR)/sub 6/ (R = i-Pr, neo-Pe, Et) and ammonia. These results are compared with other nitrido compounds of molybdenum and tungsten. Crystal data for (t-BuO)/sub 3/Mo identical with N is presented. 19 references, 3 figures, 4 tables.« less

68 citations

Journal ArticleDOI
TL;DR: Etude des proprietes reductrices des complexes suivants: HM(CO) 5 − et cis-HM(CO), 4 P(OCH 3 ) 3 − (M=Cr, W) as mentioned in this paper.
Abstract: Etude des proprietes reductrices des complexes suivants: HM(CO) 5 − et cis-HM(CO) 4 P(OCH 3 ) 3 − (M=Cr, W)

67 citations

Journal ArticleDOI
TL;DR: Etude par RPE a haute resolution des complexes [((CO) 4 M) x bpym] − (x=1,2; M=Cr,Mo,W; Bpym=bipyrimidyle-2,2'). Interpretation des resultats par une localisation electronique as discussed by the authors.
Abstract: Etude par RPE a haute resolution des complexes [((CO) 4 M) x bpym] − (x=1,2; M=Cr,Mo,W; bpym=bipyrimidyle-2,2'). Interpretation des resultats par une localisation electronique

67 citations

Journal ArticleDOI
TL;DR: In this article, the reaction of Li2(W(CO)5) with excess 13CO2 at -78 C gives (W( CO)5(13CO), confirming that the reaction involves reductive disproportionation of CO2 to CO and CO3(2-).
Abstract: : Carbon dioxide reacts readily with M2(M'(CO)5) (M = Li, Na, K, M' = W; M = K, M' = Cr, Mo, W) to give the corresponding group 6 hexacarbonyls (M(CO)6) and alkali metal carbonates. The reaction of Li2(W(CO)5) with excess 13CO2 at -78 C gives (W(CO)5(13CO)), confirming that the reaction involves reductive disproportionation of CO2 to CO and CO3(2-). The group 8 carbonylmetalates Na2(M(CO)4) (M = Fe, Ru, Os) react with CO2 to give (M(CO)5) and carbonate, and Na2(V(eta-C5H5)(CO)3) reacts with CO2 to give (V(eta-C5H5)(CO)4) and carbonate, indicating that reductive disproportionation is a general reaction of dianionic carbonylmetalates with CO2. Careful addition of one equivalent of CO2 to a solution of Li2(W(CO)5) at -78 C leads to an intermediate 1:1 adduct with an IR spectrum consistent with formulation as Li2(W(CO)5(eta 1-CO2)). The principal 13C absorption at 223.4 delta of a sample of Li2(W(CO)5(eta 1-13CO2)) prepared at -78 C exhibits Jw-c = 92 Hz, consistent with the central C being directly bonded to W and superscript 2 hybridized. Oxide scrambling from coordinated CO2 to coordinated CO at higher temperatures results in complex signals between 205 and 201 sigma assigned to the carbonyl ligands.

65 citations