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Dihydrogen Complex
Dihydrogen complexes are coordination complexes containing intact H2 as a ligand. They are a subset of sigma complexes. The prototypical complex is W(CO)3( PCy3)2(H2). This class of compounds represent intermediates in metal-catalyzed reactions involving hydrogen. Hundreds of dihydrogen complexes have been reported. Most examples are cationic transition metals complexes with octahedral geometry. Upon complexation, the H−H bond is extended to 0.81–0.82 Å as indicated by neutron diffraction, about a 10% extension relative to the H−H bond in free H2. Some complexes containing multiple hydrogen ligands, i.e. polyhydrides, also exhibit short H−H contacts. It has been suggested that distances 1 Å are better described as dihydride complexes (see figure). Characterization The usual method for characterization is 1H NMR spectroscopy. The magnitude of spin-spin coupling, ''J''HD, is a useful indicator of the strength of the bond between the hydrogen and deuterium in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Coordination Complexes
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 comple ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Relaxation (NMR)
In MRI and NMR spectroscopy, an observable nuclear spin polarization ( magnetization) is created by a homogeneous magnetic field. This field makes the magnetic dipole moments of the sample precess at the resonance ( Larmor) frequency of the nuclei. At thermal equilibrium, nuclear spins precess randomly about the direction of the applied field. They become abruptly phase coherent when they are hit by radiofrequent (RF) pulses at the resonant frequency, created orthogonal to the field. The RF pulses cause the population of spin-states to be perturbed from their thermal equilibrium value. The generated transverse magnetization can then induce a signal in an RF coil that can be detected and amplified by an RF receiver. The return of the longitudinal component of the magnetization to its equilibrium value is termed ''spin-lattice'' relaxation while the loss of phase-coherence of the spins is termed ''spin-spin'' relaxation, which is manifest as an observed free induction decay (FID). ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Difluorine Complex
A difluorine complex is a molecular complex involving a difluorine molecule (F2) and another molecule. The first example was gold heptafluoride (AuF7). Instead of being a gold(VII) compound, AuF7 is an adduct of gold pentafluoride (AuF5) and F2. This conclusion has been repeatedly supported by calculations. Unlike dihydrogen complexes, which feature η2-H2, difluorine complexes feature "end-on" or η1-F2 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 elect .... See also * dihydrogen complex References Fluorine compounds {{Coordination complexes ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Triphenylphosphine
Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to P Ph3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether. Preparation and structure Triphenylphosphine can be prepared in the laboratory by treatment of phosphorus trichloride with phenylmagnesium bromide or phenyllithium. The industrial synthesis involves the reaction between phosphorus trichloride, chlorobenzene, and sodium: :PCl3 + 3 PhCl + 6 Na → PPh3 + 6 NaCl Triphenylphosphine crystallizes in triclinic and monoclinic modification. In both cases, the molecule adopts a pyramidal structure with propeller-like arrangement of the three phenyl groups. Principal reactions with chalcogens, halogens, and acids Oxidation Triphenylphosphine undergoes slow ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Brookhart's Acid
Brookhart's acid is the salt of the diethyl ether oxonium ion and tetrakis ,5-bis(trifluoromethyl)phenylorate (BAr′4). It is a colorless solid, used as a strong acid. The compound was first reported by Volpe, Grant, and Brookhart in 1992. Preparation This compound is prepared by treatment of NaBAr′4 in diethyl ether (Et2O) with hydrogen chloride: : NaBAr′4 + HCl + 2 Et2O → (OEt2)2sup>+ + NaCl NaBAr′4 is soluble in diethyl ether, whereas sodium chloride is not. Precipitation of sodium chloride thus drives the formation of the oxonium acid compound, which is isolable as a solid. Structure and properties The acid crystallizes as a white, hygroscopic crystalline solid. NMR and elemental analysis showed that the crystal contains two equivalents of diethyl ether. In solution, the compound slowly degrades to ''m''-C6H3(CF3)2 and BAr′3. (OEt2)2B(C6F5)4] is a related compound with a slightly different weakly coordinating anion; it was first reported in 2000. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Weakly Coordinating Anion
Anions that interact weakly with cations are termed non-coordinating anions, although a more accurate term is weakly coordinating anion. Non-coordinating anions are useful in studying the reactivity of electrophilic cations. They are commonly found as counterions for cationic metal complexes with an 18-Electron rule, unsaturated coordination sphere. These special anions are essential components of Homogeneous catalysis, homogeneous Ziegler–Natta catalyst, alkene polymerisation catalysts, where the active catalyst is a coordinatively unsaturated, cationic transition metal complex. For example, they are employed as counterions for the electron counting, 14 valence electron cations [(C5H5)2ZrR]+ (R = methyl or a growing polyethylene chain). Complexes derived from non-coordinating anions have been used to catalyze hydrogenation, hydrosilylation, oligomerization, and the living polymerization of alkenes. The popularization of non-coordinating anions has contributed to increased underst ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chlorobis(dppe)iron Hydride
Chlorobis(dppe)iron hydride is a coordination complex with the formula HFeCl(dppe)2, where dppe is the bidentate ligand 1,2-bis(diphenylphosphino)ethane. It is a red-violet solid. The compound has attracted much attention as a precursor to dihydrogen complexes. Structure The complex exhibits octahedral molecular geometry. The chloride and hydride ligands are mutually trans. The bond distances between the iron metal atom and the coordinating ligands are given by the following: Synthesis and reactions The compound is synthesized according to the following idealized reaction: :FeCl2 + 2 dppe + Na H4→ NaCl + ½ B2H6 + HFeCl(dppe)2 In the course of this conversion, high-spin complex FeCl2(dppe)2 converts to low-spin HFeCl(dppe)2. The complex HFeCl dppe)2 exhibits a number of reactions associated with the remaining Fe-Cl bond. Reaction of the complex with sodium borohydride gives the dihydride complex: :HFeCl(dppe)2 + NaBH4 → H2Fe(dppe)2 + NaCl + "BH3" Removal of chl ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Agostic Interaction
In organometallic chemistry, agostic interaction refers to the interaction of a coordinatively-unsaturated transition metal with a C−H bond, when the two electrons involved in the C−H bond enter the empty d-orbital of the transition metal, resulting in a three-center two-electron bond. Many catalytic transformations, e.g. oxidative addition and reductive elimination, are proposed to proceed via intermediates featuring agostic interactions. Agostic interactions are observed throughout organometallic chemistry in alkyl, alkylidene, and polyenyl ligands. History The term agostic, derived from the Ancient Greek word for "to hold close to oneself", was coined by Maurice Brookhart and Malcolm Green, on the suggestion of the classicist Jasper Griffin, to describe this and many other interactions between a transition metal and a C−H bond. Often such agostic interactions involve alkyl or aryl groups that are held close to the metal center through an additional σ-bond.. Short ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
X-rays
An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10 Picometre, picometers to 10 Nanometre, nanometers, corresponding to frequency, frequencies in the range 30 Hertz, petahertz to 30 Hertz, exahertz ( to ) and energies in the range 145 electronvolt, eV to 124 keV. X-ray wavelengths are shorter than those of ultraviolet, UV rays and typically longer than those of gamma rays. In many languages, X-radiation is referred to as Röntgen radiation, after the German scientist Wilhelm Röntgen, Wilhelm Conrad Röntgen, who discovered it on November 8, 1895. He named it ''X-radiation'' to signify an unknown type of radiation.Novelline, Robert (1997). ''Squire's Fundamentals of Radiology''. Harvard University Press. 5th edition. . Spellings of ''X-ray(s)'' in English include the variants ''x-ray(s)'', ''xray(s)'', and ''X ray(s)''. The most familiar use of X-ra ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Neutron
The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons behave similarly within the nucleus, and each has a mass of approximately one atomic mass unit, they are both referred to as nucleons. Their properties and interactions are described by nuclear physics. Protons and neutrons are not elementary particles; each is composed of three quarks. The chemical properties of an atom are mostly determined by the configuration of electrons that orbit the atom's heavy nucleus. The electron configuration is determined by the charge of the nucleus, which is determined by the number of protons, or atomic number. The number of neutrons is the neutron number. Neutrons do not affect the electron configuration, but the sum of atomic and neutron numbers is the mass of the nucleus. Atoms of a chemical element t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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