Organotitanium Compounds
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Organotitanium Compounds
Organotitanium chemistry is the science of organotitanium compounds describing their physical properties, synthesis, and reactions. Organotitanium compounds in organometallic chemistry contain carbon-titanium chemical bonds. They are reagents in organic chemistry and are involved in major industrial processes. Brief history Although the first attempt to prepare an organotitanium compound dates back to 1861, the first example was not reported until 1954. In that year titanocene dichloride was described by Wilkinson and Birmingham. Independently, titanium-based Ziegler–Natta catalysts were described leading to major commercial applications, for which the 1963 Nobel Prize in Chemistry was awarded. This technology underscored the technical significance of organotitanium chemistry. Properties The titanium electron configuration ( rd24s2) vaguely resembles that of carbon and like carbon, the +4 oxidation state dominates. Titanium is however a much larger element than carbon, reflected ...
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Bis(cyclopentadienyl)titanium(III) Chloride
Bis(cyclopentadienyl)titanium(III) chloride, also known as the Nugent–RajanBabu reagent, is the organotitanium compound which exists as a dimer with the formula C5H5)2TiClsub>2. It is an air sensitive green solid. The complex finds specialized use in synthetic organic chemistry as a single electron reductant. In the presence of a suitable solvent that can act as a two-electron donor ("solv"), such as an ether like tetrahydrofuran, the dimer separates and forms a chemical equilibrium between the forms C5H5)2TiCland C5H5)2Ti(solv)Cl It is these forms that are responsible for much of the chemical properties of this reagent, which is also the reason that the substance is sometimes written as C5H5)2TiClor p2TiCl where Cp− represents the cyclopentadienyl anion. An example of an application of this reagent is in the preparation of vinorelbine, a chemotherapeutic agent which can be prepared in three steps from the naturally-occurring alkaloid leurosine. Synthesis and str ...
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Titanium(IV) Chloride
Titanium tetrachloride is the inorganic compound with the formula . It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide () and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula () to the word. Properties and structure is a dense, colourless distillable liquid, although crude samples may be yellow or even red-brown. It is one of the rare transition metal halides that is a liquid at room temperature, being another example. This property reflects the fact that molecules of weakly self-associate. Most metal chlorides are polymers, wherein the chloride atoms bridge between the metals. Its melting and boiling points are similar to those of . has a "closed" electronic shell, with the same nu ...
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Organic Synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one of the most important branches of organic chemistry. There are several main areas of research within the general area of organic synthesis: ''total synthesis'', ''semisynthesis'', and ''methodology''. Total synthesis A total synthesis is the complete chemical synthesis of complex organic molecules from simple, commercially available petrochemical or natural precursors. Total synthesis may be accomplished either via a linear or convergent approach. In a ''linear'' synthesis—often adequate for simple structures—several steps are performed one after another until the molecule is complete; the chemical compounds made in each step are called synthetic intermediates. Most often, each step in a synthesis refers to a separate rea ...
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Heterogeneous Catalysis
In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Phase distinguishes between not only solid, liquid, and gas components, but also immiscible mixtures (e.g. oil and water), or anywhere an interface is present. Heterogeneous catalysis typically involves solid phase catalysts and gas phase reactants. In this case, there is a cycle of molecular adsorption, reaction, and desorption occurring at the catalyst surface. Thermodynamics, mass transfer, and heat transfer influence the rate (kinetics) of reaction. Heterogeneous catalysis is very important because it enables faster, large-scale production and the selective product formation. Approximately 35% of the world's GDP is influenced by catalysis. The production of 90% of chemicals (by volume) is assisted by solid catalysts. The chemical and ...
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Ethene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds). Ethylene is widely used in the chemical industry, and its worldwide production (over 150 million tonnes in 2016) exceeds that of any other organic compound. Much of this production goes toward polyethylene, a widely used plastic containing polymer chains of ethylene units in various chain lengths. Ethylene is also an important natural plant hormone and is used in agriculture to force the ripening of fruits. The hydrate of ethylene is ethanol. Structure and properties This hydrocarbon has four hydrogen atoms bound to a pair of carbon atoms that are connected by a double bond. All six atoms that comprise ethylene are coplanar. The H-C-H angle is 117.4°, close to the 120° for ideal sp² hybridized carbon. The molecule is also relatively weak: rotati ...
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Polymerization
In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer, monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many forms of polymerization and different systems exist to categorize them. In chemical compounds, polymerization can occur via a variety of reaction mechanisms that vary in complexity due to the functional groups present in the reactants and their inherent steric effects. In more straightforward polymerizations, alkenes form polymers through relatively simple free-radical reaction, radical reactions; in contrast, reactions involving substitution at a carbonyl group require more complex synthesis due to the way in which reactants polymerize. Alkanes can also be polymerized, but only with the help of strong acids. As alkenes can polymerize in somewhat straightforward radical reactions, they form useful compounds such as polyethylene and p ...
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Diethylaluminium Chloride
Diethylaluminium chloride, abbreviated DEAC, is an organoaluminium compound. Although usually given the chemical formula (C2H5)2AlCl, it exists as a dimer, C2H5)2AlClsub>2 It is a precursor to Ziegler-Natta catalysts employed for the production of polyolefins. The compound is also a Lewis acid, useful in organic synthesis. The compound is a colorless waxy solid, but is usually handled as a solution in hydrocarbon solvents. It is highly reactive, even pyrophoric. Structure Compounds of the empirical formula AlR2Cl (R = alkyl, aryl) exist as dimers with the formula (R2Al)2(μ-Cl)2. The aluminium adopts a tetrahedral geometry. Production Diethylaluminium chloride can be produced from ethylaluminium sesquichloride, (C2H5)3Al2Cl3, by reduction with sodium: :2 (C2H5)3Al2Cl3 + 3 Na → 3 (C2H5)2AlCl + Al + 3 NaCl It is also obtained from the reaction of triethylaluminium Triethylaluminium is one of the simplest examples of an organoaluminium compound. Despite its name it has the ...
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Titanium(III) Chloride
Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins. Structure and bonding In TiCl3, each titanium atom has one ''d'' electron, rendering its derivatives paramagnetic, that is, the substance is attracted into a magnetic field. Solutions of titanium(III) chloride are violet, which arises from excitations of its ''d''-electron. The colour is not very intense since the transition is forbidden by the Laporte selection rule. Four solid forms or polymorphs of TiCl3 are known. All feature titanium in an octahedral coordination sphere. These forms can be distinguished by crystallography as well as by their magnetic properties, which probes exchange interactions. β-TiCl3 crystallizes as brown needles. Its structure consists of chains of TiCl6 octahedra tha ...
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Phenyl
In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6 H5, and is often represented by the symbol Ph. Phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen, which may be replaced by some other element or compound to serve as a functional group. Phenyl group has six carbon atoms bonded together in a hexagonal planar ring, five of which are bonded to individual hydrogen atoms, with the remaining carbon bonded to a substituent. Phenyl groups are commonplace in organic chemistry. Although often depicted with alternating double and single bonds, phenyl group is chemically aromatic and has equal bond lengths between carbon atoms in the ring. Nomenclature Usually, a "phenyl group" is synonymous with C6H5− and is represented by the symbol Ph or, archaically, Φ. Benzene is sometimes denoted as PhH. Phenyl groups are generally attached to other atoms or groups. For example, triphenylmethane (Ph3 ...
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Air-free Technique
Air-free techniques refer to a range of manipulations in the chemistry laboratory for the handling of compounds that are air-sensitive. These techniques prevent the compounds from reacting with components of air, usually water and oxygen; less commonly carbon dioxide and nitrogen. A common theme among these techniques is the use of a fine (100–10−3 Torr) or high (10−3–10−6 Torr) vacuum to remove air, and the use of an inert gas: preferably argon, but often nitrogen. The two most common types of air-free technique involve the use of a glovebox and a Schlenk line, although some rigorous applications use a high-vacuum line. In both methods, glassware (often Schlenk tubes) are pre-dried in ovens prior to use. They may be flame-dried to remove adsorbed water. Prior to coming into an inert atmosphere, vessels are further dried by ''purge-and-refill'' — the vessel is subjected to a vacuum to remove gases and water, and then refilled with inert gas. This cycle is usually r ...
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