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Nyholm-Rail Reaction
1,2-Bis(dimethylarsino)benzene (diars) is the organoarsenic compound with the formula CH(As(CH)). The molecule consists of two dimethylarsino groups attached to adjacent carbon centers of a benzene ring. It is a chelating ligand in coordination chemistry. This colourless oil is commonly abbreviated "diars." Coordination chemistry Related, but non-chelating organoarsenic ligands include triphenylarsine and trimethylarsine. Work on diars preceded the development of the chelating diphosphine ligands such as dppe, which are now prevalent in homogeneous catalysis. Diars is a bidentate ligand used in coordination chemistry. It was first described in 1939, but was popularized by R. S. Nyholm for its ability to stabilize metal complexes with unusual oxidation states and coordination numbers, e.g. TiCl(diars). High coordination numbers arise because diars is fairly compact and the As-M bonds are long, which relieves crowding at the metal center. In terms of stabilizing unusual oxidation ...
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Organoarsenic Compound
Organoarsenic chemistry is the chemistry of compounds containing a chemical bond between arsenic and carbon. A few organoarsenic compounds, also called "organoarsenicals," are produced industrially with uses as insecticides, herbicides, and fungicides. In general these applications are declining in step with growing concerns about their impact on the environment and human health. The parent compounds are arsane and arsenic acid. Despite their toxicity, organoarsenic biomolecules are well known. History 140px, Cacodyl (tetramethyldiarsine) was one of the first organoarsenic compounds. Surprising for an area now considered of minor importance, organoarsenic chemistry played a prominent role in the history of the field of chemistry. The oldest known organoarsenic compound, the foul smelling cacodyl was reported in "cacodyl" (1760) and is sometimes classified as the first synthetic organometallic compound. The compound Salvarsan was one of the first pharmaceuticals, earning a Nobel ...
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Dppe
1,2-Bis(diphenylphosphino)ethane (dppe) is an organophosphorus compound with the formula (PhPCH) (Ph = phenyl). It is a commonly used bidentate ligand in coordination chemistry. It is a white solid that is soluble in organic solvents. Preparation The preparation of dppe is by the alkylation of NaPPh: :P(CH) + 2 Na → NaP(CH) + NaCH NaP(CH), which is readily air-oxidized, is treated with 1,2-dichloroethane (ClCHCHCl) to give dppe: :2 NaP(CH) + ClCHCHCl → (CH)PCHCHP(CH) + 2 NaCl Reactions The reduction of dppe by lithium to give PhHP(CH)PHPh has been reported. :PhP(CH)PPh + 4 Li → PhLiP(CH)PLiPh + 2 PhLi Hydrolysis gives the bis(secondary phosphine): :PhLiP(CH)PLiPh + 2 PhLi + 4HO → PhHP(CH)PHPh + 4 LiOH + 2 CH : Treatment of dppe with conventional oxidants such as hydrogen peroxide (HO), aqueous bromine (Br), etc., produces dppeO in low yield (e.g., 13%) as a result of non-selective oxidation.Encyclopedia of Reagents for Organic Synthesis 2001 John Wiley & Sons, Ltd Select ...
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Benzene Derivatives
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, benzene is classed as a hydrocarbon. Benzene is a natural constituent of petroleum and is one of the elementary petrochemicals. Due to the cyclic continuous pi bonds between the carbon atoms, benzene is classed as an aromatic hydrocarbon. Benzene is a colorless and highly flammable liquid with a sweet smell, and is partially responsible for the aroma of gasoline. It is used primarily as a precursor to the manufacture of chemicals with more complex structure, such as ethylbenzene and cumene, of which billions of kilograms are produced annually. Although benzene is a major industrial chemical, it finds limited use in consumer items because of its toxicity. History Discovery The word "''benzene''" derives from "''gum benzoin''" (benzoin re ...
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1,2-Dichlorobenzene
1,2-Dichlorobenzene, or orthodichlorobenzene (ODCB), is an organic compound with the formula CHCl. This colourless liquid is poorly soluble in water but miscible with most organic solvents. It is a derivative of benzene, consisting of two adjacent chlorine atoms. It is mainly used as a precursor chemical in the synthesis of agrochemicals, as a preferred solvent for dissolving and working with fullerenes, as an insecticide, and in softening and removing carbon-based contamination on metal surfaces. Production and uses 1,2-Dichlorobenzene is obtained as a side-product of the production of chlorobenzene: : + → + HCl The reaction also affords the 1,4- and small amounts of the 1,3-isomer. The 1,4- isomer is preferred over the 1,2- isomer due to steric hindrance. The 1,3- isomer is uncommon because it is a meta- compound, while chlorine, like all halogens, is an ortho/para- director in terms of electrophilic aromatic substitution. It is mainly used as a precursor to 1,2- ...
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X-ray Crystallography
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional picture of the density of electrons within the crystal. From this electron density, the mean positions of the atoms in the crystal can be determined, as well as their chemical bonds, their crystallographic disorder, and various other information. Since many materials can form crystals—such as salts, metals, minerals, semiconductors, as well as various inorganic, organic, and biological molecules—X-ray crystallography has been fundamental in the development of many scientific fields. In its first decades of use, this method determined the size of atoms, the lengths and types of chemical bonds, and the atomic-scale differences among various mat ...
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Ronald Sydney Nyholm
Sir Ronald Sydney Nyholm (29 January 1917 – 4 December 1971) was an Australian chemist who was a leading figure in inorganic chemistry in the 1950s and 1960s. Education Born on 29 January 1917 as the fourth in a family of six children. Nyholm's father, Eric Edward Nyholm (1878–1932) was a railway guard. Nyholm's paternal grandfather, Erik Nyholm (1850–1887) was a coppersmith born in Nykarleby in the Swedish-speaking part of Finland, who migrated to Adelaide in 1873. Ronald Nyholm valued his Finnish roots and was particularly proud in his election in 1959 as Corresponding Member of the Finnish Chemical Society. Hailing from the small mining town of Broken Hill, New South Wales, he was early exposed to the role of inorganic chemistry. He attended Burke Ward Public School and Broken Hill High School. Nyholm married Maureen Richardson of Epping, a suburb of Sydney, NSW, at the parish church in Kensington, London on 6 August 1948. After graduating from Broken Hill High ...
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Joseph Chatt
Joseph Chatt (6 November 1914 – 19 May 1994) was a renowned British researcher in the area of inorganic and organometallic chemistry. His name is associated with the description of the pi-bond between transition metals and alkenes, the Dewar–Chatt–Duncanson model. Chatt received his Ph.D. at the University of Cambridge under the direction of F. G. Mann for research on organoarsenic and organophosphorus compounds and their complexes with transition metals. He was employed at Imperial Chemical Industries from 1949 to 1962, during which time he, often in collaboration with Bernard L. Shaw, published influential work on the metal hydrides and metal alkene complexes. During this period, he reported the first example of C-H bond activation by a transition metal and one of the first examples of a transition metal hydride. In the 1960s, Chatt moved to a professorship at the University of Sussex and subsequently assumed directorship of the Nitrogen Fixation Unit under the Agric ...
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Homogeneous Catalysis
In chemistry, homogeneous catalysis is catalysis by a soluble catalyst in a solution. Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution. In contrast, heterogeneous catalysis describes processes where the catalysts and substrate are in distinct phases, typically solid-gas, respectively. The term is used almost exclusively to describe solutions and implies catalysis by organometallic compounds. Homogeneous catalysis is an established technology that continues to evolve. An illustrative major application is the production of acetic acid. Enzymes are examples of homogeneous catalysts. Examples Acid catalysis The proton is a pervasive homogeneous catalyst because water is the most common solvent. Water forms protons by the process of self-ionization of water. In an illustrative case, acids accelerate (catalyze) the hydrolysis of esters: :CH3CO2CH3 + H2O CH3CO2H + CH3OH At neutral pH, aqueous solutions of most e ...
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Trimethylarsine
Trimethylarsine (abbreviated TMA or TMAs) is the chemical compound with the formula (CH3)3As, commonly abbreviated As Me3 or TMAs. This organic derivative of arsine has been used as a source of arsenic in microelectronics industry, a building block to other organoarsenic compounds, and serves as a ligand in coordination chemistry. It has distinct "garlic"-like smell. Trimethylarsine had been discovered as early as 1854. Structure and preparation AsMe3 is a pyramidal molecule. The As-C distances average 1.519 Å, and the C-As-C angles are 91.83° Trimethylarsine can be prepared by treatment of arsenic oxide with trimethylaluminium: :As2O3 + 1.5 lMe3sub>2 → 2 AsMe3 + 3/n (MeAl-O)n Occurrence and reactions Trimethylarsine is the volatile byproduct of microbial action on inorganic forms of arsenic which are naturally occurring in rocks and soils at the parts-per-million level. Trimethylarsine has been reported only at trace levels (parts per billion) in landfill gas from Germany, C ...
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Chemical Formula
In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, such as parentheses, dashes, brackets, commas and ''plus'' (+) and ''minus'' (−) signs. These are limited to a single typographic line of symbols, which may include Subscript and superscript, subscripts and superscripts. A chemical formula is not a chemical nomenclature, chemical name, and it contains no words. Although a chemical formula may imply certain simple chemical structures, it is not the same as a full chemical structural formula. Chemical formulae can fully specify the structure of only the simplest of molecules and chemical substances, and are generally more limited in power than chemical names and structural formulae. The simplest types of chemical formulae are called ''empirical formulae'', which use letters and numbers ind ...
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Triphenylarsine
Triphenylarsine is the chemical compound with the formula As(C6H5)3. This organoarsenic compound, often abbreviated As Ph3, is a colorless crystalline solid that is used as a ligand and a reagent in coordination chemistry and organic synthesis. The molecule is pyramidal with As-C distances of 1.942–1.956 Å and C-As-C angles of 99.6–100.5°. This compound is prepared by the reaction of arsenic trichloride with chlorobenzene using sodium as the reducing agent: :AsCl3 + 3 PhCl + 6 Na → AsPh3 + 6 NaCl Reactions Reaction of triphenylarsine with lithium gives lithium diphenylarsenide: :AsPh3 + 2 Li → LiAsPh2 + LiPh Triphenylarsine is the precursor to tetraphenylarsonium chloride, sPh4l, a popular precipitating agent. AsPh3 forms metal complexes with metals. Most are analogues of the corresponding triphenylphosphine derivatives. Examples include IrCl(CO)(AsPh3)2, RhCl(AsPh3)3, and Fe(CO)4(AsPh3). Tetraphenylarsonium chloride Tetraphenylarsonium chloride is ...
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Coordination Chemistry
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many metal-containing compounds, especially those that include transition metals (elements like titanium that belong to the Periodic Table's d-block), are coordination complexes. Nomenclature and terminology Coordination complexes are so pervasive that their structures and reactions are described in many ways, sometimes confusingly. The atom within a ligand that is bonded to the central metal atom or ion is called the donor atom. In a typical complex, a metal ion is bonded to several donor atoms, which can be the same or different. A polydentate (multiple bonded) ligand is a molecule or ion that bonds to the central atom through several of the ligand's atoms; ligands with 2, 3, 4 or even 6 bonds to the central atom are common. These compl ...
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