The Organometallic and Metal-Organic Chemistry of Molybdenum
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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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
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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TL;DR: In this article, the structure of the C5H5H2H5 complex was refined to R = 0.053 (R′= 0.052) for 2 526 reflections (230 K) to 2θ⩽ 50° (Mo-KαX-radiation).
Abstract: Reaction of [Mo(CO)(η2-MeC2Me)2(η-C5H5)][BF4] with lithium dimethylcuprate affords [Mo(CO)(η2-MeC2Me)(σ-CMeCMe2)(η-C5H5)], whereas reaction with K[BHBus3] followed by treatment with CO gives [[graphic omitted])C(Me)CHMe}(CO)2(η-C5H5)], which has been identified by X-ray crystallography. Crystals are monoclinic, space group P21/n, Z= 4, in a unit cell with a= 6.495(3), b= 16.902(9), c= 14.002(7)A, β= 97.62(4)°. The structure has been refined to R= 0.025 (R′= 0.024) for 2 136 reflections (293 K) to 2θ < 55°(Mo-KαX-radiation). The molybdenum atom is co-ordinated by an η-C5H5 ligand, two terminal linear carbonyl ligands, and a bidentate ligand derived from one CO, two but-2-yne molecules, and a hydride ligand. Reaction of CO with [Mo(CO)(η2-MeC2Me)(σ-CMeCMe2)(η-C5H5)] affords an analogous complex. A similar reaction between K[BHBus3] and [Mo(CO)(η2-EtC2Me)2(η-C5H5)][BF4] gives two analogous isomeric complexes, both isomers containing the vinyl group, C(Me)CHEt. In contrast [Mo(CO)(η2-ButC2H)2(η-C5H5)][BF4] affords the lactone complex [Mo{η3:η2-HButCCH[graphic omitted]H}(CO)(η-C5H5)] characterised by X-ray crystallography. Crystals are monoclinic, space group P21/c(no. 14), Z= 4, in a unit cell with a= 11.935(7), b= 11.673(9), c= 13.674(9)A, β= 105.93(5)°. The structure has been refined to R= 0.053 (R′= 0.052) for 2 526 reflections (230 K) to 2θ⩽ 50°(Mo-KαX-radiation). The molybdenum atom is bound to an η-cyclopentadienyl ligand and a linear terminal CO. The remainder of the co-ordination sphere is taken up by an η3 : η2 vinyl-substituted, unsaturated γ-lactone derived from one hydride, two carbonyls, and two ButC2H ligands. The structures of these complexes and the mechanism of their formation are discussed.
24 citations
TL;DR: A series of dimolybdenum and ditungsten pentafluorophenoxides has been prepared by alcoholysis of M 2 (NMe 2 ) 6 (M=Mo, W) with P 2 (NH 2 Me 2 ) 2 ] as discussed by the authors.
Abstract: A series of dimolybdenum and ditungsten pentafluorophenoxides has been prepared by alcoholysis of M 2 (NMe 2 ) 6 (M=Mo, W) with pentafluorophenol. Mo 2 (OC 6 F 5 ) 4 (NMe 2 ) 2 (NHMe 2 ) 2 has been isolated both from the reaction of Mo 2 (NMe 2 ) 6 with pentafluorophenol and as a disproportionation product. The crystals are different but contain molecules with essentially identical structural features. From reactions with pentafluorophenol, only low yields of Mo 2 (OC 6 F 5 ) 4 (NHMe 2 ) 4 and[(NH 2 Me 2 ) 2 ][Mo 2 O 2 (μ−O) 2 (OC 6 F 5 ) 4 ] have been isolated, both of which are structurally characterized
24 citations
24 citations