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Berry Pseudorotation Mechanism
The Berry mechanism, or Berry pseudorotation mechanism, is a type of vibration causing molecules of certain geometries to isomerize by exchanging the two axial ligands (see Figure at right) for two of the equatorial ones. It is the most widely accepted mechanism for pseudorotation and most commonly occurs in trigonal bipyramidal molecules such as PF5, though it can also occur in molecules with a square pyramidal geometry. The Berry mechanism is named after R. Stephen Berry, who first described this mechanism in 1960.RS Berry, 1960, "Correlation of rates of intramolecular tunneling processes, with application to some Group V compounds," ''J. Chem. Phys.'' 32:933-938, DOI 10.1063/1.1730820; seo accessed 28 May 2014M Cass, KK Hii & HS Rzepa, 2005, "Mechanisms that interchange axial and equatorial atoms in fluxional processes: Illustration of the Berry pseudorotation, the turnstile and the lever mechanisms via animation of transition state normal vibrational modes", ''J. Chem. Educ. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Isomerization
In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomerization. When the isomerization occurs intramolecularly it may be called a rearrangement reaction. When the activation energy for the isomerization reaction is sufficiently small, both isomers will exist in a temperature-dependent equilibrium with each other. Many values of the standard free energy difference, \Delta G^\circ, have been calculated, with good agreement between observed and calculated data. Examples and applications Alkanes Skeletal isomerization occurs in the cracking process, used in the petrochemical industry. As well as reducing the average chain length, straight-chain hydrocarbons are converted to branched isomers in the process, as illustrated the following reaction of ''n''-butane to ''i''-butane. :\overset -> \o ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Pseudorotation
In chemistry, a pseudorotation is a set of intramolecular movements of attached groups (i.e., ligands) on a highly symmetric molecule, leading to a molecule indistinguishable from the initial one. The International Union of Pure and Applied Chemistry (IUPAC) defines a pseudorotation as a " ereoisomerization resulting in a structure that ''appears'' to have been produced by rotation of the entire initial molecule", the result of which is a "product" that is "superposable on the initial one, unless different positions are distinguished by substitution, including isotopic substitution." Well-known examples are the intramolecular isomerization of trigonal bipyramidal compounds by the Berry pseudorotation mechanism, and the out-of-plane motions of carbon atoms exhibited by cyclopentane, leading to the interconversions it experiences between its many possible conformers (envelope, twist). Note, no angular momentum is generated by this motion. In these and related examples, a small d ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Trigonal Bipyramidal Molecular Geometry
In chemistry, a trigonal bipyramid formation is a molecular geometry with one atom at the center and 5 more atoms at the corners of a triangular bipyramid. This is one geometry for which the bond angles surrounding the central atom are not identical (see also pentagonal bipyramid), because there is no geometrical arrangement with five terminal atoms in equivalent positions. Examples of this molecular geometry are phosphorus pentafluoride (), and phosphorus pentachloride () in the gas phase. Axial (or apical) and equatorial positions The five atoms bonded to the central atom are not all equivalent, and two different types of position are defined. For phosphorus pentachloride as an example, the phosphorus atom shares a plane with three chlorine atoms at 120° angles to each other in ''equatorial'' positions, and two more chlorine atoms above and below the plane (''axial'' or ''apical'' positions). According to the VSEPR theory of molecular geometry, an axial position is more crowd ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Square Pyramidal
In molecular geometry, square pyramidal geometry describes the shape of certain compounds with the formula where L is a ligand. If the ligand atoms were connected, the resulting shape would be that of a pyramid with a square base. The point group symmetry involved is of type C4v. The geometry is common for certain main group compounds that have a stereochemically-active lone pair, as described by VSEPR theory. Certain compounds crystallize in both the trigonal bipyramidal and the square pyramidal structures, notably . As a transition state in Berry pseudorotation As a trigonal bipyramidal molecule undergoes Berry pseudorotation, it proceeds via an intermediary stage with the square pyramidal geometry. Thus even though the geometry is rarely seen as the ground state, it is accessed by a low energy distortion from a trigonal bipyramid. Pseudorotation also occurs in square pyramidal molecules. Molecules with this geometry, as opposed to trigonal bipyramidal, exhibit heavier ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
KK Hii
King Kuok "Mimi" Hii (born 23 December 1969) is a chemist whose fields of research include application of catalysis to organic synthesis. She is the Director of Imperial College London's Centre for Rapid Online Analysis of Reactions (ROAR). Academic career Hii studied for both her BSc and PhD at The University of Leeds investigating multidentate ligand metal complexes under the supervision of Bernard L. Shaw. Postdoctoral studies at Oxford University in John M. Brown's group were followed by independent research at University of Leeds, Kings College London and in Imperial College London. In 2016 she was awarded a Professorship in Catalysis and in 2018 became the Director of the Centre for Rapid Online Analysis of Reactions. Research interests Hii has investigated catalysis during her research career. In Oxford, she characterised intermediates of the Heck reaction. Hii also studied this reaction at King's College London. Hii has continued with this field of study producing ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Square Pyramidal Molecular Geometry
In molecular geometry, square pyramidal geometry describes the shape of certain compounds with the formula where L is a ligand. If the ligand atoms were connected, the resulting shape would be that of a pyramid with a square base. The point group symmetry involved is of type C4v. The geometry is common for certain main group compounds that have a stereochemically-active lone pair, as described by VSEPR theory. Certain compounds crystallize in both the trigonal bipyramidal and the square pyramidal structures, notably . As a transition state in Berry pseudorotation As a trigonal bipyramidal molecule undergoes Berry pseudorotation, it proceeds via an intermediary stage with the square pyramidal geometry. Thus even though the geometry is rarely seen as the ground state, it is accessed by a low energy distortion from a trigonal bipyramid. Pseudorotation also occurs in square pyramidal molecules. Molecules with this geometry, as opposed to trigonal bipyramidal, exhibit heavier ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Berry Pseudorotation
The Berry mechanism, or Berry pseudorotation mechanism, is a type of vibration causing molecules of certain geometries to isomerize by exchanging the two axial ligands (see Figure at right) for two of the equatorial ones. It is the most widely accepted mechanism for pseudorotation and most commonly occurs in trigonal bipyramidal molecules such as PF5, though it can also occur in molecules with a square pyramidal geometry. The Berry mechanism is named after R. Stephen Berry, who first described this mechanism in 1960.RS Berry, 1960, "Correlation of rates of intramolecular tunneling processes, with application to some Group V compounds," ''J. Chem. Phys.'' 32:933-938, DOI 10.1063/1.1730820; seo accessed 28 May 2014M Cass, KK Hii & HS Rzepa, 2005, "Mechanisms that interchange axial and equatorial atoms in fluxional processes: Illustration of the Berry pseudorotation, the turnstile and the lever mechanisms via animation of transition state normal vibrational modes", ''J. Chem. Educ. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Iodine Pentafluoride
Iodine pentafluoride is an interhalogen compound with chemical formula IF5. It is one of the fluorides of iodine. It is a colorless liquid, although impure samples appear yellow. It is used as a fluorination reagent and even a solvent in specialized syntheses. Preparation It was first synthesized by Henri Moissan in 1891 by burning solid iodine in fluorine gas. This exothermic reaction is still used to produce iodine pentafluoride, although the reaction conditions have been improved. :I2 + 5 F2 → 2 IF5 Reactions IF5 reacts vigorously with water forming hydrofluoric acid and iodic acid: :IF5 + 3 H2O → HIO3 + 5 HF Upon treatment with fluorine, it converts to iodine heptafluoride: :IF5 + F2 → IF7 It has been used as a solvent for handling metal fluorides. For example, the reduction of osmium hexafluoride to osmium pentafluoride with iodine is conducted in a solution in iodine pentafluoride: :10 OsF6 + I2 → 10 OsF5 + 2 IF5 Primary amines react with iodine pentafluo ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Pseudorotation
In chemistry, a pseudorotation is a set of intramolecular movements of attached groups (i.e., ligands) on a highly symmetric molecule, leading to a molecule indistinguishable from the initial one. The International Union of Pure and Applied Chemistry (IUPAC) defines a pseudorotation as a " ereoisomerization resulting in a structure that ''appears'' to have been produced by rotation of the entire initial molecule", the result of which is a "product" that is "superposable on the initial one, unless different positions are distinguished by substitution, including isotopic substitution." Well-known examples are the intramolecular isomerization of trigonal bipyramidal compounds by the Berry pseudorotation mechanism, and the out-of-plane motions of carbon atoms exhibited by cyclopentane, leading to the interconversions it experiences between its many possible conformers (envelope, twist). Note, no angular momentum is generated by this motion. In these and related examples, a small d ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Bailar Twist
The Bailar twist is a mechanism proposed for the racemization of octahedral complexes containing three bidentate chelate rings. Such complexes typically adopt an octahedral molecular geometry, in which case they possess helical chirality. One pathway by which these compounds can racemize is via the formation of a trigonal prismatic intermediate with D3h point group symmetry. This pathway is named in honor of John C. Bailar, Jr., an inorganic chemist who investigated this process.{{cite journal , author = A. Rodger, B. F. G. Johnson , title = Which is more likely: the Ray–Dutt twist or the Bailar twist? , journal = Inorganic Chemistry , year = 1988 , volume = 27 , issue = 18 , pages = 3061–3062 , doi =10.1021/ic00291a001 An alternative pathway is called the Ray–Dutt twist. See also * Pseudorotation * Bartell mechanism * Berry mechanism * Ray–Dutt twist * Fluxional molecule In chemistry and molecular physics, fluxional (or non-rigid) molecules are molecules t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
