Triiron Dodecacarbonyl
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Triiron Dodecacarbonyl
Triiron dodecacarbonyl is the organoiron compound with the formula Fe3(CO)12. It is a dark green solid that sublimes under vacuum. It is soluble in nonpolar organic solvents to give intensely green solutions. Most low-nuclearity clusters are pale yellow or orange. Hot solutions of Fe3(CO)12 decompose to an iron mirror, which can be pyrophoric in air. The solid decomposes slowly in air, and thus samples are typically stored cold under an inert atmosphere. It is a more reactive source of iron(0) than iron pentacarbonyl. Synthesis It was one of the first metal carbonyl clusters synthesized. It was occasionally obtained from the thermolysis of Fe(CO)5: :3 Fe(CO)5 → Fe3(CO)12 + 3 CO Traces of the compound are easily detected because of its characteristic deep green colour. UV-photolysis of Fe(CO)5 produces Fe2(CO)9, not Fe3(CO)12. The usual synthesis of Fe3(CO)12 starts with the reaction of Fe(CO)5 with base: :3 Fe(CO)5 + (C2H5)3N + H2O → C2H5)3NHHFe3(CO)11] + 3 CO + CO2 f ...
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Triruthenium Dodecacarbonyl
Triruthenium dodecacarbonyl is the chemical compound with the formula Ru3(CO)12. Classified as metal carbonyl cluster, it is a dark orange-colored solid that is soluble in nonpolar organic solvents. The compound serves as a precursor to other organoruthenium compounds. Structure and synthesis The cluster has ''D3h'' symmetry, consisting of an equilateral triangle of Ru atoms, each of which bears two axial and two equatorial CO ligands. The Ru-Ru distance is 284 pm. Os3(CO)12 has the same structure. In Fe3(CO)12, two CO ligands are bridging, resulting in C2v symmetry. In solution, is fluxional as indicated by the observation of a single CO signal in the room temperature 13C NMR spectrum. The barrier is estimated at 20 kJ/mol is prepared by treating solutions of ruthenium trichloride with carbon monoxide in the presence of a base. Dichlororuthenium tricarbonyl dimer is an intermediate. The stoichiometry of the reaction is uncertain, one possibility being the following ...
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Walter Hieber
Walter Hieber (18 December 1895 – 29 November 1976) was an inorganic chemist, known as the father of metal carbonyl chemistry. He was born 18 December 1895 and died 29 November 1976. Hieber's father was Johannes Hieber, an influential evangelical minister and politician. Hieber was educated at Tübingen, Würzburg, and Heidelberg. In 1935 he was appointed Director of the Inorganic Chemical Institute at the Technical University in Münich. Among his numerous research findings, Hieber prepared the first metal carbonyl hydrides such as H2Fe(CO)4 and HMn(CO)5. He discovered that metal carbonyls undergo nucleophilic attack by hydroxide, the “Hieber base reaction.” He and his students discovered several metal carbonyl compounds such as Re2(CO)10 and Os3(CO)12 He pioneered the development of metal carbonyl sulfides.Hieber, W. and Scharfenberg, C., "Einwirkung organischer Schwefelverbindungen auf die Carbonyls des Eisens", Chemische Berichte, 1940, volume 73, pages 10 ...
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Disproportionation
In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation state. The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called ''comproportionation'', also known as ''symproportionation''. More generally, the term can be applied to any desymmetrizing reaction where two molecules of one type react to give one each of two different types: : This expanded definition is not limited to redox reactions, but also includes some molecular autoionization reactions, such as the self-ionization of water. In contrast, some authors use the term ''redistribution'' to refer to reactions of this type (in either direction) when only ligand exchange but no redox is involved and distinguish such processes from disproportionation and comproportionati ...
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Metal Carbido Complex
A metal carbido complex is a coordination complex that contains a carbon atom as a ligand. They are analogous to Metal nitrido complex, metal nitrido complexes. Carbido complexes are a molecular subclass of Carbide, carbides, which are prevalent in organometallic and inorganic chemistry. Carbido complexes represent models for intermediates in Fischer–Tropsch synthesis, olefin metathesis, and related catalytic industrial processes. Ruthenium-based carbido complexes are by far the most synthesized and characterized to date. Although, complexes containing chromium, gold, iron, nickel, molybdenum, osmium, rhenium, and tungsten cores are also known. Mixed-metal carbides are also known. Carbido clusters Most molecular carbido complexes are clusters, usually featuring carbide as a six-fold bridging ligand. Examples include [Rhodium, Rh6C(CO)15]2−, and [Ruthenium, Ru6C(CO)16]2−. Though exceptions exist, such as the nonanuclear Ruthenium cluster (μ-C)Ru9(CO)14 (μ3-η5: η2:η2-C9H7) ...
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Bis(triphenylphosphine)iron Tricarbonyl
Tricarbonylbis(triphenylphosphine)iron(0) is a coordination complex with the formula Fe(CO)3(PPh3)2 (Ph = C6H5). A yellow solid, this complex is derived from iron pentacarbonyl by replacement of two carbonyl ligands by triphenylphosphine (PPh3). Synthesis and reactions The title complex can be prepared by reaction of triiron dodecacarbonyl with excess triphenylphosphine: : (Triphenylphosphine)iron tetracarbonyl is an intermediate in the synthesis of this compound. The title complex can also be produced more efficiently by borohydride-catalyzed substitution of iron pentacarbonyl. Protonation gives the ferrous hydride: : Both the mono- and bis(triphenylphosphine) complexes were originally described by Walter Reppe. References

{{reflist Triphenylphosphine complexes Iron carbonyl complexes ...
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(Triphenylphosphine)iron Tetracarbonyl
(Triphenylphosphine)iron tetracarbonyl is a coordination complex with the formula Fe(CO)4(PPh3) (Ph = C6H5). An off-white solid, this complex is derived from iron pentacarbonyl by replacement of one carbonyl ligand by triphenylphosphine (PPh3). Synthesis and use The title complex can be prepared by reaction of iron pentacarbonyl or triiron dodecacarbonyl with triphenylphosphine: : The substitution is catalyzed by cobalt chloride. (Triphenylphosphine)iron tetracarbonyl is an intermediate in the synthesis of bis(triphenylphosphine)iron tricarbonyl. Both the mono- and bis(triphenylphosphine) complexes were originally employed in pioneering research on homogeneous catalysis by 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 Un .... References {{DEFAULTSORT:Triphenylphosph ...
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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 versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. 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 thre ...
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Diborane
Diborane(6), commonly known as diborane, is the chemical compound with the formula . It is a highly toxic, colorless, and pyrophoric gas with a repulsively sweet odor. Given its simple formula, borane is a fundamental boron compound. It has attracted wide attention for its electronic structure. Several of its derivatives are useful reagents. Structure and bonding The structure of diborane has D2h symmetry. Four hydrides are terminal, while two bridge between the boron centers. The lengths of the B–Hbridge bonds and the B–Hterminal bonds are 1.33 and 1.19 Å respectively. This difference in bond lengths reflects the difference in their strengths, the B–Hbridge bonds being relatively weaker. The weakness of the B–Hbridge compared to B–Hterminal bonds is indicated by their vibrational signatures in the infrared spectrum, being ≈2100 and 2500 cm−1 respectively. The model determined by molecular orbital theory describes the bonds between boron and the te ...
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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 ...
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Triosmium Dodecacarbonyl
Triosmium dodecacarbonyl is a chemical compound with the formula Os3(CO)12. This yellow-colored metal carbonyl cluster is an important precursor to organo-osmium compounds. Many of the advances in cluster chemistry have arisen from studies on derivatives of Os3(CO)12 and its lighter analogue Ru3(CO)12. Structure and synthesis The cluster has D3h symmetry, consisting of an equilateral triangle of Os atoms, each of which bears two axial and two equatorial CO ligands. Each of the three osmium centers has an octahederal structure with four CO ligands and the other two osmium atoms. The Os–Os bond distance is 2.88 Å (288 pm). Ru3(CO)12 has the same structure, whereas Fe3(CO)12 is different, with two bridging CO ligands resulting in C2v symmetry. In solution, is fluxional as indicated by 13C NMR measurements. The barrier is estimated at 70 kJ/mol Os3(CO)12 is prepared by the direct reaction of OsO4 with carbon monoxide at 175 °C under high pressures: : 3 OsO4 + ...
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Triruthenium Dodecacarbonyl
Triruthenium dodecacarbonyl is the chemical compound with the formula Ru3(CO)12. Classified as metal carbonyl cluster, it is a dark orange-colored solid that is soluble in nonpolar organic solvents. The compound serves as a precursor to other organoruthenium compounds. Structure and synthesis The cluster has ''D3h'' symmetry, consisting of an equilateral triangle of Ru atoms, each of which bears two axial and two equatorial CO ligands. The Ru-Ru distance is 284 pm. Os3(CO)12 has the same structure. In Fe3(CO)12, two CO ligands are bridging, resulting in C2v symmetry. In solution, is fluxional as indicated by the observation of a single CO signal in the room temperature 13C NMR spectrum. The barrier is estimated at 20 kJ/mol is prepared by treating solutions of ruthenium trichloride with carbon monoxide in the presence of a base. Dichlororuthenium tricarbonyl dimer is an intermediate. The stoichiometry of the reaction is uncertain, one possibility being the following ...
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Molecular Symmetry
In chemistry, molecular symmetry describes the symmetry present in molecules and the classification of these molecules according to their symmetry. Molecular symmetry is a fundamental concept in chemistry, as it can be used to predict or explain many of a molecule's chemical property, chemical properties, such as whether or not it has a molecular dipole moment, dipole moment, as well as its allowed spectroscopy, spectroscopic transitions. To do this it is necessary to use group theory. This involves classifying the states of the molecule using the irreducible representations from the character table of the symmetry group of the molecule. Symmetry is useful in the study of molecular orbitals, with applications to the Hückel method, to ligand field theory, and to the Woodward–Hoffmann rules. Many university level textbooks on physical chemistry, quantum chemistry, spectroscopy and inorganic chemistry discuss symmetry. Another framework on a larger scale is the use of crystal sy ...
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