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Dichlorobis(triphenylphosphine)nickel(II)
Dichlorobis(triphenylphosphine)nickel(II) refers to a pair of metal phosphine complexes with the formula NiCl2 (C6H5)3sub>2. The compound exists as two isomers, a paramagnetic dark blue solid and a diamagnetic red solid. These complexes function as catalysts for organic synthesis.Montgomery, J. Science of Synthesis Georg Thiene Verlag KG, Vol. 1, p 11, CODEN: SSCYJ9 Synthesis and structure The blue isomer is prepared by treating hydrated nickel chloride with triphenylphosphine in alcohols or glacial acetic acid: :NiCl2•6H2O + 2 PPh3 → NiCl2(PPh3)2 + 6 H2O When allowed to crystallise from chlorinated solvents, the tetrahedral isomer converts to the square planar isomer. The square planar form is red and diamagnetic. The phosphine ligands are trans with respective Ni-P and Ni-Cl distances of 2.24 and 2.17 Å. The blue form is paramagnetic and features tetrahedral Ni(II) centers. In this isomer, the Ni-P and Ni-Cl distances are elongated at 2.32 and 2.21 Å. As illustrated by ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Bis(triphenylphosphine)palladium(II) Chloride
Bis(triphenylphosphine)palladium chloride is a coordination compound of palladium containing two triphenylphosphine and two chloride ligands. It is a yellow solid that is soluble in some organic solvents. It is used for palladium-catalyzed coupling reactions, e.g. the Sonogashira–Hagihara reaction. The complex is Square planar molecular geometry, square planar. Many analogous complexes are known with different phosphine ligands. Preparation and reactions This compound may be prepared by treating palladium(II) chloride with triphenylphosphine: :PdCl2 + 2 PPh3 → PdCl2(PPh3)2 Upon reduction with hydrazine in the presence of excess triphenylphosphine, the complex is a precursor to tetrakis(triphenylphosphine)palladium, Pd(PPh3)4: :2 PdCl2(PPh3)2 + 4 PPh3 + 5 N2H4 → 2 Pd(PPh3)4 + N2 + 4 N2H5+Cl− Structure Several crystal structures containing PdCl2(PPh3)2 have been reported. In all of the structures, PdCl2(PPh3)2 adopts a Square planar molecular geometry, square ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Metal Phosphine Complex
A metal-phosphine complex is a In coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0). Preparation Many metal phosphine complexes are prepared by reactions of metal halides with preformed phosphines. For example, treatment of a suspension of palladium chloride in ethanol with triphenylphosphine yields monomeric bis(triphenylphosphine)palladium(II) chloride units. :[PdCl2]n + 2PPh3 → PdCl2(PPh3)2 The first reported phosphine complexes were ''cis''- and ''trans''-PtCl2(PEt3)2 reported by Cahours and Gal in 1870. Often the phosphine serves both as a ligand and as a reductant. This property is illustrated by the synthesis of many platinum-metal complexes of triphenylphos ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Bis(triphenylphosphine)platinum(II) Chloride
Bis(triphenylphosphine)platinum chloride is a metal phosphine complex with the formula PtCl2 (C6H5)3sub>2. Cis- and trans isomers are known. The cis isomer is a white crystalline powder, while the trans isomer is yellow. Both isomers are square planar about the central platinum atom. The cis isomer is used primarily as a reagent for the synthesis of other platinum compounds. Preparation The cis isomer is the prepared by heating solutions of platinum(II) chlorides with triphenylphosphine. For example, starting from potassium tetrachloroplatinate: :K2PtCl4 + 2 PPh3 → ''cis''-Pt(PPh3)2Cl2 + 2 KCl The trans isomer is the prepared by treating potassium trichloro(ethylene)platinate(II) (Zeise's salt) with triphenylphosphine: :KPt(C2H4)Cl3 + 2 PPh3 → ''trans''-Pt(PPh3)2Cl2 + KCl + C2H4 With heating or in the presence of excess PPh3, the trans isomer converts to the cis complex. The latter complex is the thermodynamic product due to triphenylphosphine being a strong trans effect ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. Catalysis may be classified as either homogeneous, whose components are dispersed in the same phase (usually gaseous or liquid) as the reactant, or heterogeneous, whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some stag ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organic Synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one of the most important branches of organic chemistry. There are several main areas of research within the general area of organic synthesis: '' total synthesis'', ''semisynthesis'', and ''methodology''. Total synthesis A total synthesis is the complete chemical synthesis of complex organic molecules from simple, commercially available petrochemical or natural precursors. Total synthesis may be accomplished either via a linear or convergent approach. In a ''linear'' synthesis—often adequate for simple structures—several steps are performed one after another until the molecule is complete; the chemical compounds made in each step are called synthetic intermediates. Most often, each step in a synthesis refers to a separate rea ... [...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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Cis–trans Isomerism
''Cis''–''trans'' isomerism, also known as geometric isomerism or configurational isomerism, is a term used in chemistry that concerns the spatial arrangement of atoms within molecules. The prefixes "''cis''" and "''trans''" are from Latin: "this side of" and "the other side of", respectively. In the context of chemistry, ''cis'' indicates that the functional groups (substituents) are on the same side of some plane, while ''trans'' conveys that they are on opposing (transverse) sides. ''Cis''–''trans'' isomers are stereoisomers, that is, pairs of molecules which have the same formula but whose functional groups are in different orientations in three-dimensional space. ''Cis-trans'' notation does not always correspond to ''E''–''Z'' isomerism, which is an ''absolute'' stereochemical description. In general, ''cis''–''trans'' stereoisomers contain double bonds that do not rotate, or they may contain ring structures, where the rotation of bonds is restricted or prevented ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Spectrochemical Series
A spectrochemical series is a list of ligands ordered by ligand "strength", and a list of metal ions based on oxidation number, group and element. For a metal ion, the ligands modify the difference in energy Δ between the d orbitals, called the ligand-field splitting parameter in ligand field theory, or the crystal-field splitting parameter in crystal field theory. The splitting parameter is reflected in the ion's electronic and magnetic properties such as its spin state, and optical properties such as its color and absorption spectrum. Spectrochemical series of ligands The spectrochemical series was first proposed in 1938 based on the results of absorption spectra of cobalt complexes. A partial ''spectrochemical series'' listing of ligands from small Δ to large Δ is given below. (For a table, see the ligand page.) :I− < Br− < S2− < SCN− (S–bonded) < Cl− < N3− < F−< NCO− < OH− < C2O42− < O [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Steric Effect
Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivity of ions and molecules. Steric effects complement electronic effects, which dictate the shape and reactivity of molecules. Steric repulsive forces between overlapping electron clouds result in structured groupings of molecules stabilized by the way that opposites attract and like charges repel. Steric hindrance Steric hindrance is a consequence of steric effects. Steric hindrance is the slowing of chemical reactions due to steric bulk. It is usually manifested in ''intermolecular reactions'', whereas discussion of steric effects often focus on ''intramolecular interactions''. Steric hindrance is often exploited to control selectivity, such as slowing unwanted side-reactions. Steric hindrance between adjacent groups can also affect torsional ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Walter Reppe
Walter Julius Reppe (29 July 1892 in Göringen – 26 July 1969 in Heidelberg) was a German chemist. He is notable for his contributions to the chemistry of acetylene. Education and career Walter Reppe began his study of the natural sciences University of Jena in 1911. Interrupted by the First World War, he obtained his doctorate in Munich in 1920. In 1921, Reppe worked for BASF's main laboratory. From 1923, he worked on the catalytic dehydration of formamide to prussic acid in the indigo laboratory, developing this procedure for industrial use. In 1924, he left research for 10 years, only resuming it in 1934. Acetylene chemistry Reppe began his interest in acetylene in 1928. Acetylene is a gas which can take part in many chemical reactions. However, it is explosive and accidents often occurred. Because of this danger, small quantities of acetylene were used at a time, and always without high pressures. In fact, it was forbidden to compress acetylene over 1.5 bar at ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alkyne Trimerisation
In organic chemistry, an alkyne trimerisation is a +2+2nbsp; cycloaddition reaction in which three alkyne units () react to form a benzene ring. The reaction requires a metal catalyst. The process is of historic interest as well as being applicable to organic synthesis. Being a cycloaddition reaction, it has high atom economy. Many variations have been developed, including cyclisation of mixtures of alkynes and alkenes as well as alkynes and nitriles. Mechanism and stereochemistry Trimerisation of acetylene to benzene is highly exergonic, proceeding with a free energy change of 142 kcal/mol at room temperature. Kinetic barriers however prevent the reaction from proceeding smoothly. The breakthrough came in 1948, when Reppe and Schweckendiek reported their wartime results showing that nickel compounds are effective catalysts: : 3 RC2H -> C6R3H3 Since this discovery, many other cyclotrimerisations have been reported. Mechanism In terms of mechanism, the reactions beg ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Carbonylation
Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains. Organic chemistry Several industrially useful organic chemicals are prepared by carbonylations, which can be highly selective reactions. Carbonylations produce organic carbonyls, i.e., compounds that contain the C=O functional group such as aldehydes, carboxylic acids and esters. Carbonylations are the basis of many types of reactions, including hydroformylation and Reppe reactions. These reactions require metal catalysts, which bind and activate the CO. These processes involve transition metal acyl complexes as intermediates. Much of this theme was developed by Walter Reppe. Hydroformylation Hydroformylation entails the addition of both carbon monoxide and hydrogen to unsaturated ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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