Transition Metal Pyridine Complexes
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Transition Metal Pyridine Complexes
Transition metal pyridine complexes encompass many coordination complexes that contain pyridine as a ligand. Most examples are mixed-ligand complexes. Many variants of pyridine are also known to coordinate to metal ions, such as the methylpyridines, quinolines, and more complex rings. Bonding With a pKa of 5.25 for its conjugate acid, pyridine is about 15x less basic than imidazole. Pyridine is a weak pi-acceptor ligand. Trends in the M-N distances for complexes of the type Cl2(py)4sup>2+ reveal an anticorrelation with d-electron count. Few low-valent metal complexes of pyridines are known. The role of pyridine as a Lewis base extends also to main group chemistry. Examples include sulfur trioxide pyridine complex SO3(py) and pyridine adduct of borane, BH3py. Classification of metal-pyridine complexes Many metal pyridine complexes are known. These complexes can be classified according to their geometry, i.e. octahedral, tetrahedral, linear, etc. Octahedral complexes Chloro( ...
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Ru(NH3)5py(OTf)2Xray
''Ru, ru, or RU may refer to: Russia * Russia (ISO 3166-1 alpha-2 country code) * Russian language (ISO 639 alpha-2 code) * .ru, the Internet country code top-level domain for Russia China * Rù (入), the entering tone in Chinese language phonetics * Rú (儒), a Chinese language term for Confucianism * Ru (surname) (茹), a Chinese surname * Ru River (汝), in Henan, China * Ru ware, a type of Chinese pottery Educational institutions * Radboud University Nijmegen, in Nijmegen, Netherlands * Radford University, in Virginia, USA * Rai University in Gujarat, India * Rajshahi University in Bangladesh * Rama University in India * Ramkhamhaeng University in Thailand * Regis University in Colorado, USA * Reykjavík University Iceland * Rhodes University in Grahamstown, South Africa * Rockefeller University in New York, USA * Rockhurst University in Missouri, USA * Roosevelt University in Chicago, Illinois, USA * Rowan University in New Jersey, USA * Ruse University in ...
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Steric Effects
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 ...
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Organocobalt Chemistry
Organocobalt chemistry is the chemistry of organometallic compounds containing a carbon to cobalt chemical bond. Organocobalt compounds are involved in several organic reactions and the important biomolecule vitamin B12 has a cobalt-carbon bond. Many organocobalt compounds exhibit useful catalytic properties, the preeminent example being dicobalt octacarbonyl. Alkyl complexes Most fundamental are the cobalt complexes with only alkyl ligands. Examples include Co(4-norbornyl)4 and its cation. Alkylcobalt is represented by vitamin B12 and related enzymes. In methylcobalamin the ligand is a methyl group, which is electrophilic. in vitamin B12, the alkyl ligand is an adenosyl group. Related to vitamin B12 are cobalt porphyrins, dimethylglyoximates, and related complexes of Schiff base ligands. These synthetic compounds also form alkyl derivatives that undergo diverse reactions reminiscent of the biological processes. The weak cobalt(III)-carbon bond in vitamin B12 analogues ...
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Grignard Reagent
A Grignard reagent or Grignard compound is a chemical compound with the general formula , where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride and phenylmagnesium bromide . They are a subclass of the organomagnesium compounds. Grignard compounds are popular reagents in organic synthesis for creating new carbon-carbon bonds. For example, when reacted with another halogenated compound in the presence of a suitable catalyst, they typically yield and the magnesium halide as a byproduct; and the latter is insoluble in the solvents normally used. In this aspect, they are similar to organolithium reagents. Pure Grignard reagents are extremely reactive solids. They are normally handled as solutions in solvents such as diethyl ether or tetrahydrofuran; which are relatively stable as long as water is excluded. In such a medium, a Grignard reagent is invariably present as a complex with the magnesium atom conn ...
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Crabtree's Catalyst
Crabtree's catalyst is an organoiridium compound with the formula [1,5-Cyclooctadiene, C8H12IrTricyclohexylphosphine, P(C6H11)3pyridine, C5H5N]PF6. It is a homogeneous catalyst for hydrogenation and hydrogen-transfer reactions, developed by Robert H. Crabtree. This air stable orange solid is commercially available and known for its directed hydrogenation to give trans stereoselectivity with respective of directing group. Structure and synthesis The complex has a square planar molecular geometry, as expected for a d8 complex. It is prepared from cyclooctadiene iridium chloride dimer. Reactivity Crabtree’s catalyst is effective for the hydrogenations of mono-, di-, tri-, and tetra-substituted substrates. Whereas Wilkinson’s catalyst and the Schrock–Osborn catalyst do not catalyze the hydrogenation of a tetrasubstituted olefin, Crabtree’s catalyst does so to at high turnover frequencies (table). : The catalyst is reactive at room temperature. The reaction is robust without ...
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Imidazole
Imidazole (ImH) is an organic compound with the formula C3N2H4. It is a white or colourless solid that is soluble in water, producing a mildly alkaline solution. In chemistry, it is an aromatic heterocycle, classified as a diazole Diazole refers to either one of a pair of isomeric chemical compounds with molecular formula C3H4N2, having a five-membered ring consisting of three carbon atoms and two nitrogen atoms.
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Cis-Dichlorobis(bipyridine)ruthenium(II)
''cis''-Dichlorobis(bipyridine)ruthenium(II) is the coordination complex with the formula RuCl2(bipy)2, where bipy is 2,2'-bipyridine. It is a dark green diamagnetic solid that is a precursor to many other complexes of ruthenium, mainly by substitution of the two chloride ligands. The compound has been crystallized as diverse hydrates. Synthesis and structure The complex is prepared by heating a DMF solution of ruthenium trichloride and bipyridine. With octahedral coordination geometry, the complex exists exclusively as the chiral Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from ... cis isomer. The corresponding Ru(III) salts are also known.{{cite journal, title=Structural Variations Induced by Changes in Oxidation State and Their Role in Electron Transfer. Crystal and Molecular ...
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Noninnocent Ligand
In chemistry, a (redox) non-innocent ligand is a ligand in a metal complex where the oxidation state is not clear. Typically, complexes containing non-innocent ligands are redox active at mild potentials. The concept assumes that redox reactions in metal complexes are either metal or ligand localized, which is a simplification, albeit a useful one. C.K. Jørgensen first described ligands as "innocent" and "suspect": "Ligands are innocent when they allow oxidation states of the central atoms to be defined. The simplest case of a suspect ligand is NO..." Redox reactions of complexes of innocent vs. non-innocent ligands Conventionally, redox reactions of coordination complexes are assumed to be metal-centered. The reduction of MnO4− to MnO42− is described by the change in oxidation state of manganese from 7+ to 6+. The oxide ligands do not change in oxidation state, remaining 2-. Oxide is an innocent ligand. Another example of conventional metal-centered redox couple is ...
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2,2'-Bipyridine
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Picoline
Picoline refers to any of three isomers of methylpyridine (CH3C5H4N). They are all colorless liquids with a characteristic smell similar to that of pyridine. They are miscible with water and most organic solvents. The CAS number of an unspecified picoline isomer is 333-41-1 The methyl group in 2- and 4- picolines is reactive; e.g., 2-picolines condenses with acetaldehyde in the presence of warm aqueous sodium hydroxide to form 2-propenylpyridine. History Picoline was obtained, in impure form, in 1826 by the German chemist Otto Unverdorben (1806 – 1873), who obtained it by the pyrolysis (roasting) of bones. He called it ''Odorin'' due to its unpleasant smell. In 1849, the Scottish chemist Thomas Anderson (1819 – 1874) prepared picoline in pure form, from coal tar and via the pyrolysis of bones. Anderson also named picoline by combining the Latin words ''pix'' (tar) and ''oleum'' (oil) because coal tar oil was a source of picoline. By 1870, the German chemist Adolf von Ba ...
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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 ...
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