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Fluxional Molecule
In chemistry and molecular physics, fluxional (or non-rigid) molecules are molecules that undergo dynamics such that some or all of their atoms interchange between symmetry-equivalent positions. Because virtually all molecules are fluxional in some respects, e.g. bond rotations in most organic compounds, the term fluxional depends on the context and the method used to assess the dynamics. Often, a molecule is considered fluxional if its spectroscopic signature exhibits line-broadening (beyond that dictated by the Heisenberg uncertainty principle) due to chemical exchange. In some cases, where the rates are slow, fluxionality is not detected spectroscopically, but by isotopic labeling and other methods. Spectroscopic studies Many organometallic compounds exhibit fluxionality. Fluxionality is, however, pervasive. NMR spectroscopy Temperature dependent changes in the NMR spectra result from dynamics associated with the fluxional molecules when those dynamics proceed at rates compar ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemistry
Chemistry is the scientific study of the properties and behavior of matter. It is a physical science within the natural sciences that studies the chemical elements that make up matter and chemical compound, compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during chemical reaction, reactions with other chemical substance, substances. Chemistry also addresses the nature of chemical bonds in chemical compounds. In the scope of its subject, chemistry occupies an intermediate position between physics and biology. It is sometimes called the central science because it provides a foundation for understanding both Basic research, basic and Applied science, applied scientific disciplines at a fundamental level. For example, chemistry explains aspects of plant growth (botany), the formation of igneous rocks (geology), how atmospheric ozone is formed and how environmental pollutants are degraded (ecology), the prop ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electron Transfer
Electron transfer (ET) occurs when an electron relocates from an atom, ion, or molecule, to another such chemical entity. ET describes the mechanism by which electrons are transferred in redox reactions. Electrochemical processes are ET reactions. ET reactions are relevant to photosynthesis and respiration and commonly involve transition metal complexes. In organic chemistry ET is a step in some industrial polymerization reactions. It is foundational to photoredox catalysis. Classes of electron transfer Inner-sphere electron transfer In inner-sphere ET, two redox centers are covalently linked during the ET. This bridge can be permanent, in which case the electron transfer event is termed intramolecular electron transfer. More commonly, however, the covalent linkage is transitory, forming just prior to the ET and then disconnecting following the ET event. In such cases, the electron transfer is termed intermolecular electron transfer. A famous example of an inner sphere ET pr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sulfur Tetrafluoride
Sulfur tetrafluoride is a chemical compound with the formula S F4. It is a colorless corrosive gas that releases dangerous hydrogen fluoride gas upon exposure to water or moisture. Sulfur tetrafluoride is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries. Structure Sulfur in SF4 is in the +4 oxidation state, with one lone pair of electrons. The atoms in SF4 are arranged in a see-saw shape, with the sulfur atom at the center. One of the three equatorial positions is occupied by a nonbonding lone pair of electrons. Consequently, the molecule has two distinct types of F ligands, two axial and two equatorial. The relevant bond distances are = 164.3 pm and = 154.2 pm. It is typical for the axial ligands in hypervalent molecules to be bonded less strongly. The 19F NMR spectrum of SF4 reveals only one signal, which indicates that the axial and equatorial F ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Iron Pentacarbonyl
Iron pentacarbonyl, also known as iron carbonyl, is the compound with formula . Under standard conditions Fe( CO)5 is a free-flowing, straw-colored liquid with a pungent odour. Older samples appear darker. This compound is a common precursor to diverse iron compounds, including many that are useful in small scale organic synthesis. Properties Iron pentacarbonyl is a homoleptic metal carbonyl, where carbon monoxide is the only ligand complexed with a metal. Other examples include octahedral chromium hexacarbonyl (Cr(CO)6) and tetrahedral nickel carbonyl (Ni(CO)4). Most metal carbonyls have 18 valence electrons, and Fe(CO)5 fits this pattern with 8 valence electrons on Fe and five pairs of electrons provided by the CO ligands. Reflecting its symmetrical structure and charge neutrality, Fe(CO)5 is volatile; it is one of the most frequently encountered liquid metal complexes. Fe(CO)5 adopts a trigonal bipyramidal structure with the Fe atom surrounded by five CO ligands: thr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Berry Mechanism
The Berry mechanism, or Berry pseudorotation mechanism, is a type of vibration causing molecules of certain geometries to isomerization, isomerize by exchanging the two axial ligands (see the figure) for two of the equatorial ones. It is the most widely accepted mechanism for pseudorotation and most commonly occurs in trigonal bipyramidal molecular geometry, trigonal bipyramidal molecules such as PF5, 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.R. S. Berry, 1960"Correlation of rates of intramolecular tunneling processes, with application to some Group V compounds" ''J. Chem. Phys.'' 32:933–938, ; accessed 28 May 2014.M. Cass, Mimi Hii, K. K. Hii, H. S. 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 ... [...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 " stereoisomerization 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 smal ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Fluorine-19 Nuclear Magnetic Resonance Spectroscopy
Fluorine-19 nuclear magnetic resonance spectroscopy (fluorine NMR or 19F NMR) is an analytical technique used to detect and identify fluorine-containing compounds. 19F is an important nucleus for NMR spectroscopy because of its receptivity and large chemical shift dispersion, which is greater than that for proton nuclear magnetic resonance spectroscopy. Operational details 19F has a nuclear spin (I) of and a high gyromagnetic ratio. Consequently, this isotope is highly responsive to NMR measurements. Furthermore, 19F comprises 100% of naturally occurring fluorine. The only other highly sensitive spin NMR-active nuclei that are monoisotopic (or nearly so) are 1H and 31P. Indeed, the 19F nucleus is the third most receptive NMR nucleus, after the 3H nucleus and 1H nucleus. The 19F NMR chemical shifts span a range of about 800 ppm. For ''organo''fluorine compounds the range is narrower, being about −50 to −70 ppm (for CF3 groups) to −200 to −220 ppm ( ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phosphorus Pentafluoride
Phosphorus pentafluoride is a chemical compound with the chemical formula . It is a phosphorus halide. It is a colourless, toxic gas that fumes in air. Preparation Phosphorus pentafluoride was first prepared in 1876 by the fluorination of phosphorus pentachloride using arsenic trifluoride, which remains a favored method: : Phosphorus pentafluoride can be prepared by direct combination of phosphorus and fluorine: : Structure Single-crystal X-ray studies indicate that the has trigonal bipyramidal geometry. Thus it has two distinct types of P−F bonds (axial and equatorial): the length of an axial P−F bond is distinct from the equatorial P−F bond in the solid phase, but not the liquid or gas phases due to Berry pseudo rotation. Fluorine-19 NMR spectroscopy, even at temperatures as low as , fails to distinguish the axial from the equatorial fluorine environments. The apparent equivalency arises from the low barrier for pseudorotation via the Berry mechanism, by which th ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Proton NMR
Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the structure of its molecules. In samples where natural hydrogen (H) is used, practically all the hydrogen consists of the isotope 1H (hydrogen-1; i.e. having a proton for a nucleus). Simple NMR spectra are recorded in solution, and solvent protons must not be allowed to interfere. Deuterated (deuterium = 2H, often symbolized as D) solvents especially for use in NMR are preferred, e.g. deuterated water, D2O, deuterated acetone, (CD3)2CO, deuterated methanol, CD3OD, deuterated dimethyl sulfoxide, (CD3)2SO, and deuterated chloroform, CDCl3. However, a solvent without hydrogen, such as carbon tetrachloride, CCl4 or carbon disulfide, CS2, may also be used. Historically, deuterated solvents were supplied with a small amount (typically 0.1%) of ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemical Equilibrium
In a chemical reaction, chemical equilibrium is the state in which both the Reagent, reactants and Product (chemistry), products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the Thermodynamic system, system. This state results when the forward reaction proceeds at the same rate as the Reversible reaction, reverse reaction. The reaction rates of the forward and backward reactions are generally not zero, but they are equal. Thus, there are no net changes in the concentrations of the reactants and products. Such a state is known as dynamic equilibrium. It is the subject of study of ''equilibrium chemistry''. Historical introduction The Concept learning, concept of chemical equilibrium was developed in 1803, after Claude Louis Berthollet, Berthollet found that some chemical reactions are Reversible reaction, reversible. For any reaction mixture to exist at equilibrium, the reaction rate, ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
