1,5-Diaza-3,7-diphosphacyclooctanes
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1,5-Diaza-3,7-diphosphacyclooctanes
1,5-Diaza-3,7-diphosphacyclooctanes are organophosphorus compounds with the formula 'NCHP(R)CH often abbreviated PN. They are air-sensitive white solids that are soluble in organic solvents. The ligands exist as meso and d,l-diastereomers, but only the meso forms function as bidentate ligands. Some metal-PN complexes catalyze the hydrogen evolution reaction as well as the oxidation of hydrogen (H). The catalytic mechanism involves the interaction of substrate with the amines in the second coordination sphere. Synthesis and reactions The ligands are prepared by the condensation of a primary phosphine, formaldehyde, and a primary amine: :2 RPH + 4 CHO + 2 RNH → NCHP(R')CH + 4 HO Diazadiphosphacyclooctanes function as chelating diphos phine ligands. Typical nickel complexes contain two such ligands are give the formula i(PN) Cationic complexes of these PN and related ligands often exhibit enhanced reactivity toward H. These complexes serve as electrocatalysts for ...
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Diphosphines
Diphosphines, sometimes called bisphosphanes, are organophosphorus compounds most commonly used as bidentate phosphine ligands in inorganic and organometallic chemistry. They are identified by the presence of two phosphino groups linked by a backbone, and are usually chelating. A wide variety of diphosphines have been synthesized with different linkers and R-groups. Alteration of the linker and R-groups alters the electronic and steric properties of the ligands which can result in different coordination geometries and catalytic behavior in homogeneous catalysts. Synthesis 222px, Chlorodiisopropylphosphine is a popular building block for the preparation of diphosphines. From phosphide building blocks Many widely used diphosphine ligands have the general formula Ar2P(CH2)nPAr2. These compounds can be prepared from the reaction of X(CH2)nX (X=halogen) and MPPh2 (M = alkali metal): :Cl(CH2)nCl + 2 NaPPh2 → Ph2P(CH2)nPPh2 + 2 NaCl Diphosphine ligands can also be prepare ...
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Second Coordination Sphere
In coordination chemistry, the first coordination sphere refers to the array of molecules and ions (the ligands) directly attached to the central metal atom. The second coordination sphere consists of molecules and ions that attached in various ways to the first coordination sphere. First coordination sphere The first coordination sphere refers to the molecules that are attached directly to the metal. The interactions between the first and second coordination spheres usually involve hydrogen-bonding. For charged complexes, ion pairing is important. In hexamminecobalt(III) chloride ( o(NH3)6l3), the cobalt cation plus the 6 ammonia ligands comprise the first coordination sphere. The coordination sphere of this ion thus consists of a central MN6 core "decorated" by 18 N−H bonds that radiate outwards. Second coordination sphere Metal ions can be described as consisting of series of two concentric coordination spheres, the first and second. More distant from the second coor ...
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P2N2ligand
P, or p, is the sixteenth letter of the Latin alphabet, used in the modern English alphabet, the alphabets of other western European languages and others worldwide. Its name in English is ''pee'' (pronounced ), plural ''pees''. History The Semitic Pê (mouth), as well as the Greek Π or π ( Pi), and the Etruscan and Latin letters that developed from the former alphabet, all symbolized , a voiceless bilabial plosive. Use in writing systems In English orthography and most other European languages, represents the sound . A common digraph in English is , which represents the sound , and can be used to transliterate ''phi'' in loanwords from Greek. In German, the digraph is common, representing a labial affricate . Most English words beginning with are of foreign origin, primarily French, Latin and Greek; these languages preserve Proto-Indo-European initial *p. Native English cognates of such words often start with , since English is a Germanic language and thus has ...
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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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Diastereomer
In stereochemistry, diastereomers (sometimes called diastereoisomers) are a type of stereoisomer. Diastereomers are defined as non-mirror image, non-identical stereoisomers. Hence, they occur when two or more stereoisomers of a compound have different configurations at one or more (but not all) of the equivalent (related) stereocenters and are not mirror images of each other. When two diastereoisomers differ from each other at only one stereocenter, they are epimers. Each stereocenter gives rise to two different configurations and thus typically increases the number of stereoisomers by a factor of two. Diastereomers differ from enantiomers in that the latter are pairs of stereoisomers that differ in all stereocenters and are therefore mirror images of one another. Enantiomers of a compound with more than one stereocenter are also diastereomers of the other stereoisomers of that compound that are not their mirror image (that is, excluding the opposing enantiomer). Diastereomers h ...
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Bidentate 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 chem ...
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Chelate Complex
Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These ligands are called chelants, chelators, chelating agents, or sequestering agents. They are usually organic compounds, but this is not a necessity, as in the case of zinc and its use as a maintenance therapy to prevent the absorption of copper in people with Wilson's disease. Chelation is useful in applications such as providing nutritional supplements, in chelation therapy to remove toxic metals from the body, as contrast agents in MRI scanning, in manufacturing using homogeneous catalysts, in chemical water treatment to assist in the removal of metals, and in fertilizers. Chelate effect The chelate effect is the greater affinity of chelating ligands for a metal ion than that of similar nonchelating (monodentate) ligands for the same metal. ...
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Hydrogen Evolution Reaction
Hydrogen evolution reaction (HER) is a chemical reaction that yields H2. The conversion of protons to H2 requires reducing equivalents and usually a catalyst. In nature, HER is catalyzed by hydrogenase enzymes. Commercial electrolyzers typically employ platinum metal as the catalyst. HER is useful for producing hydrogen gas, providing a clean-burning fuel. HER, however, can also be an unwelcome side reaction that competes with other reductions such as nitrogen fixation and electrochemical reduction of carbon dioxide The electrochemical reduction of carbon dioxide, also known as electrolysis of carbon dioxide, is the conversion of carbon dioxide () to more reduction (chemistry), reduced chemical species using electrical energy. It is one possible step in the b .... References {{electrolysis Electrolysis Energy engineering ...
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Hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, and highly combustible. Hydrogen is the most abundant chemical substance in the universe, constituting roughly 75% of all normal matter.However, most of the universe's mass is not in the form of baryons or chemical elements. See dark matter and dark energy. Stars such as the Sun are mainly composed of hydrogen in the plasma state. Most of the hydrogen on Earth exists in molecular forms such as water and organic compounds. For the most common isotope of hydrogen (symbol 1H) each atom has one proton, one electron, and no neutrons. In the early universe, the formation of protons, the nuclei of hydrogen, occurred during the first second after the Big Bang. The emergence of neutral hydrogen atoms throughout the universe occurred about 370,000 ...
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Formaldehyde
Formaldehyde ( , ) (systematic name methanal) is a naturally occurring organic compound with the formula and structure . The pure compound is a pungent, colourless gas that polymerises spontaneously into paraformaldehyde (refer to section Forms below), hence it is stored as an aqueous solution (formalin), which is also used to store animal specimens. It is the simplest of the aldehydes (). The common name of this substance comes from its similarity and relation to formic acid. Formaldehyde is an important precursor to many other materials and chemical compounds. In 1996, the installed capacity for the production of formaldehyde was estimated at 8.7 million tons per year. It is mainly used in the production of industrial resins, e.g., for particle board and coatings. Forms Formaldehyde is more complicated than many simple carbon compounds in that it adopts several diverse forms. These compounds can often be used interchangeably and can be interconverted. *Molecular formald ...
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Phine
Phine District is a district (''muang'') of Savannakhet province in southern Laos Laos (, ''Lāo'' )), officially the Lao People's Democratic Republic ( Lao: ສາທາລະນະລັດ ປະຊາທິປະໄຕ ປະຊາຊົນລາວ, French: République démocratique populaire lao), is a socialist .... References Districts of Savannakhet province {{Laos-geo-stub ...
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