Triethylphosphine
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Triethylphosphine
Triethylphosphine is the organophosphorus compound with the formula P(CH2CH3)3, commonly abbreviated as PEt3. It is a colorless liquid with an unpleasant odor characteristic of alkylphosphines. The compound is a common ligand in organometallic chemistry, such as in auranofin. Structure and simple reactions It is a pyramidal molecule with approximate ''C''3''v'' symmetry. PEt3 is usually prepared using Grignard reagents: : 3 CH3CH2MgCl + P(OC6H5)3 → P(CH2CH3)3 + 3 C6H5OMgCl PEt3 reacts with strong acids to give salts PEt3.Annette Schier and Hubert Schmidbaur "P-Donor Ligands" in Encyclopedia of Inorganic Chemistry 2006, Wiley-VCH, Weinheim. This reaction is reversible. Similarly, it is also easily alkylated to give phosphonium derivatives. PEt3 is easily oxidised to the phosphine oxide with oxygen. Coordination chemistry Triethylphosphine is a highly basic ligand that forms coordination complexes with many metals. As a ligand, triethylphosphine's Tolman cone angle i ...
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Ligand Cone Angle
In coordination chemistry, the ligand cone angle (a common example being the Tolman cone angle or ''θ'') is a measure of the steric bulk of a ligand in a transition metal coordination complex. It is defined as the solid angle formed with the metal at the vertex and the outermost edge of the van der Waals spheres of the ligand atoms at the perimeter of the cone (see figure). Tertiary phosphine ligands are commonly classified using this parameter, but the method can be applied to any ligand. The term ''cone angle'' was first introduced by Chadwick A. Tolman, a research chemist at DuPont. Tolman originally developed the method for phosphine ligands in nickel complexes, determining them from measurements of accurate physical models. Asymmetric cases The concept of cone angle is most easily visualized with symmetrical ligands, e.g. PR3. But the approach has been refined to include less symmetrical ligands of the type PRR′R″ as well as diphosphines. In such asymmetric cases, th ...
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Trimethylphosphine
Trimethylphosphine is a neutral organophosphorus compound with the formula P(CH3)3, commonly abbreviated as PMe3. This colorless liquid has a strongly unpleasant odor, characteristic of alkylphosphines. The compound is a common ligand in coordination chemistry. Structure and bonding It is a pyramidal molecule with approximate ''C''3''v'' symmetry. The C–P–C bond angles are approximately 98.6°. The C–P–C bond angles are consistent with the notion that phosphorus predominantly uses the 3p orbitals for forming bonds and that there is little sp hybridization of the phosphorus atom. The latter is a common feature of the chemistry of phosphorus. As a result, the lone pair of trimethylphosphine has predominantly s-character as is the case for phosphine, PH3. PMe3 can be prepared by the treatment of triphenyl phosphite with methylmagnesium chloride: : 3 CH3MgCl + P(OC6H5)3 → P(CH3)3 + 3 C6H5OMgCl The synthesis is conducted in dibutyl ether, from which the more volatile PMe3 ...
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Hydrogen Peroxide
Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3%–6% by weight) in water for consumer use, and in higher concentrations for industrial use. Concentrated hydrogen peroxide, or " high-test peroxide", decomposes explosively when heated and has been used as a propellant in rocketry. Hydrogen peroxide is a reactive oxygen species and the simplest peroxide, a compound having an oxygen–oxygen single bond. It decomposes slowly when exposed to light, and rapidly in the presence of organic or reactive compounds. It is typically stored with a stabilizer in a weakly acidic solution in a dark bottle to block light. Hydrogen peroxide is found in biological systems including the human body. Enzymes that use or decompose hydrogen peroxide are classified as peroxidases. Properties The boiling poi ...
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Sodium Hypochlorite
Sodium hypochlorite (commonly known in a dilute solution as bleach) is an Inorganic chemistry, inorganic chemical compound with the chemical formula, formula NaOCl (or NaClO), comprising a sodium cation () and a hypochlorite anion (or ). It may also be viewed as the sodium salt (chemistry), salt of hypochlorous acid. The anhydrous Chemical compound, compound is unstable and may decompose explosively. It can be crystallized as a hydrate, pentahydrate ·5, a pale greenish-yellow solid which is not explosive and is stable if kept refrigerated. Sodium hypochlorite is most often encountered as a pale greenish-yellow dilute solution referred to as liquid bleach, which is a household chemical widely used (since the 18th century) as a disinfectant or a bleaching agent. In solution, the compound is unstable and easily decomposes, liberating chlorine, which is the active principle of such products. Sodium hypochlorite is the oldest and still most important chlorine-releasing compounds, chl ...
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Phosphine Oxide
Phosphine oxides are phosphorus compounds with the formula OPX3. When X = alkyl or aryl, these are organophosphine oxides. Triphenylphosphine oxide is an example. An inorganic phosphine oxide is phosphoryl chloride (POCl3). Structure and bonding Tertiary phosphine oxides Tertiary phosphine oxides are the most commonly encountered phosphine oxides. With the formula R3PO, they are tetrahedral compounds. They are usually prepared by oxidation of tertiary phosphines. The P-O bond is short and polar. According to molecular orbital theory, the short P–O bond is attributed to the donation of the lone pair electrons from oxygen p-orbitals to the antibonding phosphorus-carbon bonds. The nature of the P–O bond was once hotly debated. Some discussions invoked a role for phosphorus-centered d-orbitals in bonding, but this analysis is not supported by computational analyses. In terms of simple Lewis structure, the bond is more accurately represented as a dative bond, as is currently us ...
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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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Hydride Complex
Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H−-like character (e.g., ZnH2). Classes of metal hydrides Binary metal hydrides Many transition metals form compounds with hydrogen, called binary hydrides: binary, because these compounds contain only two elements, and hydride, because the hydrogenic ligand is assumed to have hydridic (H−-like) character. These compounds are invariably insoluble in all solvents, reflecting their polymeric structures. They often exhibit metal-like electrical conductivity. Many are nonstoichiometric compounds. Electropositive metals ( Ti, Zr, Hf, Zn) and some other metals form hydrides with the stoichiometry MH or sometimes MH2 (M = Ti, Zr, Hf, V, Zn). The b ...
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Organophosphorus Compound
Organophosphorus compounds are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents. Organophosphorus chemistry is the corresponding science of the properties and reactivity of organophosphorus compounds. Phosphorus, like nitrogen, is in group 15 of the periodic table, and thus phosphorus compounds and nitrogen compounds have many similar properties. The definition of organophosphorus compounds is variable, which can lead to confusion. In industrial and environmental chemistry, an organophosphorus compound need contain only an organic substituent, but need not have a direct phosphorus-carbon (P-C) bond. Thus a large proportion of pesticides (e.g., malathion), are often included in this class of compounds. Phosphorus can adopt ...
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Ligand
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical areas, including bioinorganic and medicinal chemistry, homogeneous catalysis, and environmental chemi ...
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Coordination Complex
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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Phosphonium
In polyatomic cations with the chemical formula (where R is a hydrogen or an alkyl, aryl, or halide group). These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions. Types of phosphonium cations Protonated phosphines The parent phosphonium is as found in the iodide salt, phosphonium iodide. Salts of the parent are rarely encountered, but this ion is an intermediate in the preparation of the industrially useful tetrakis(hydroxymethyl)phosphonium chloride: :PH3 + HCl + 4 CH2O → Many organophosphonium salts are produced by protonation of primary, secondary, and tertiary phosphines: :PR3 + H+ → The basicity of phosphines follows the usual trends, with R = alkyl being more basic than R = aryl. Tetraorganophosphonium cations The most common phosphonium compounds have four organic substituents attached to phosphorus. The quaternary phosphonium cations include tetraphenylphosphonium, (C6H5)4P+ and tetramethylphosphoni ...
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