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
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TL;DR: In this article, a review is concerned with the neglected class of inorganic compounds, which contain ions of the same element in two different formal states of oxidation, and a number of references cite that many individual examples of this class have been studied, yet they have very rarely been treated as a class, and there has never before, to our knowledge, been a systematic attempt to classify their properties in terms of their electronic and molecular structures.
Abstract: Publisher Summary This review is concerned with the neglected class of inorganic compounds, which contain ions of the same element in two different formal states of oxidation. Although the number of references cited in our review show that many individual examples of this class have been studied, yet they have very rarely been treated as a class, and there has never before, to our knowledge, been a systematic attempt to classify their properties in terms of their electronic and molecular structures. In the past, systems containing an element in two different states of oxidation have gone by various names, the terms “mixed valence,” nonintegral valence,” “mixed oxidation,” “oscillating valency,” and “controlled valency” being used interchangeably. Actually, none of these is completely accurate or all-embracing, but in our hope to avoid the introduction of yet another definition, we have somewhat arbitrarily adopted the phrase “mixed valence” for the description of these systems. The concept of resonance among various valence bond structures is one of the cornerstones of modern organic chemistry.
2,208 citations
TL;DR: In this article, a lecture dedicated to the late Robert B. Woodward, a supreme patterner of chaos, was given. And it is our collaboration on orbital symmetry conservation, the electronic factors which govern the course of chemical reactions, which is recognized by half of the 1981 Nobel Prize in Chemistry.
Abstract: Robert B. Woodward, a supreme patterner of chaos, was one of my teachers. I dedicate this lecture to him, for it is our collaboration on orbital symmetry conservation, the electronic factors which govern the course of chemical reactions, which is recognized by half of the 1981 Nobel Prize in Chemistry. From Woodward I learned much: the significance of the experimental stimulus to theory, the craft of constructing explanations, and the importance of asethetics in science. I will try to show you how these characteristics of chemical theory may be applied to the construction of conceptual bridges between inorganic and organic chemistry.
1,126 citations
TL;DR: In this paper, a precursor to imido alkylidene complexes that is related to 2 has been prepared by the sequence MoO{sub 2} {yields} MoO(NAr)Cl{sub 3} (dme = 1,2-dimethoxyethane) and Me{ sub 3}SiNHAr (Ar = 2,6-diisopropylphenyl) yields Mo(C-t-Bu)(NHAr), which upon treatment with a catalytic amount of NEt-sub 3] is transformed into
Abstract: The reaction between Mo(C-t-Bu)(dme)Cl{sub 3} (dme = 1,2-dimethoxyethane) and Me{sub 3}SiNHAr (Ar = 2,6-diisopropylphenyl) yields Mo(C-t-Bu)(NHAr)Cl{sub 2}(dme) (1), which upon treatment with a catalytic amount of NEt{sub 3} is transformed into Mo(CH-t-Bu)(NAr)Cl{sub 2}(dme) (2). Complexes of the type Mo(CH-t-Bu)(NAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2}, OCMe{sub 2}(CF{sub 3}), O-t-Bu, or OAr) have been prepared from 2. Complexes of the type Mo(C-t-Bu)(NHAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2} or OAr) have been prepared from 1, but they cannot be transformed into Mo(CH-t-Bu)(NAr)(OR){sub 2} complexes. A precursor to imido alkylidene complexes that is related to 2 has been prepared by the sequence MoO{sub 2} {yields} MoO{sub 2}Cl{sub 2} {yields} Mo(NAr){sub 2}Cl{sub 2} {yields} Mo(NAr){sub 2}(CH{sub 2}R{prime}){sub 2} {yields} Mo(CHR{prime})(NAr)(OTf){sub 2}(dme) (R{prime} = t-Bu or CMe{sub 2}Ph; OTf = OSO{sub 2}CF{sub 3}). Mo(CH-t-Bu)(NAr)(OTf){sub 2}(dme) crystallizes in the space group P{anti 1} with a = 17.543 {angstrom}, b = 19.008 {angstrom}, c = 9.711 {angstrom}, {alpha} = 91.91{degree}, {beta} = 99.30{degree}, {gamma} = 87.27{degree}, Z = 4, M{sub r} = 729.60, V = 3,191.1 {angstrom}{sup 3}, {rho}(calcd) = 1.518 g cm{sup {minus}3}.
928 citations
673 citations
TL;DR: In this article, the first isolable transition-metal complexes containing a coordinated dihydrogen molecule was reported, characterized by a variety of spectroscopic and structural methods to possess n/sup 2/bonded hydrogen.
Abstract: Reported were the first examples of isolable transition-metal complexes containing a coordinated dihydrogen molecule, characterized by a variety of spectroscopic and structural methods to possess n/sup 2/-bonded hydrogen. The dihydrogen ligand is symmetrically coordinated in an n/sup 2/ mode with average tungsten-hydrogen distances of 1.95 (23) angstroms (x-ray) and 1.75 angstroms (neutron, ..delta..F). The H-H separation is 0.75 (16) angstrom (x-ray) and 0.84 angstroms (neutron, ..delta..F), slightly larger than that obtained from free H/sub 2/ (0.74 angstroms). The H/sub 2/ ligand axis is approximately parallel to the trans phosphorous-phosphorus direction. Vibrational spectra of solid samples of the H/sub 2/, D/sub 2/, and HD forms (M = W) are consistent with coordination of molecular H/sub 2/. The H/sub 2/ complexes are significant in that they may represent an arrested form of oxidative addition of H/sub 2/ to metals. 1 table (DP)
625 citations