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Tuck-in Complex
In organometallic chemistry, a tuck-in complex usually refers to derivatives of Cp* ligands wherein a methyl group is deprotonated and the resulting methylene attaches to the metal. The C5–CH2–M angle is acute. The term "tucked in" was coined to describe derivatives of organotungsten complexes. Although most "tucked-in" complexes are derived from Cp* ligands, other pi-bonded rings undergo similar reactions. Scope and bonding The "tuck-in" process is related to ortho-metalation in the sense that it is an intramolecular cyclometalation. Tuck-in complexes derived from Cp* ligands are derivatives of tetramethylfulvene, sometimes abbreviated Me4Fv. A variety of complexes are known for Me4Fv and related ligands. In these complexes, the Fv can serve as a 4-electron or as a 6-electron ligand. Examples The original example proceeded via sequential loss of two equivalents of H2 from decamethyltungstocene dihydride, Cp*2WH2. The first dehydrogenation step affords a simple tuck- ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organometallic Chemistry
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide (metal carbonyls), cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term " metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are repres ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Cp* Ligand
1,2,3,4,5-Pentamethylcyclopentadiene is a cyclic diene with the formula C5Me5H (Me = CH3). 1,2,3,4,5-Pentamethylcyclopentadiene is the precursor to the ligand ''1,2,3,4,5-pentamethylcyclopentadienyl'', which is often denoted Cp* (C5Me5) and read as "C P star", the "star" signifying the five methyl groups radiating from the core of the ligand. In contrast to less-substituted cyclopentadiene derivatives, Cp*H is not prone to dimerization. Synthesis Pentamethylcyclopentadiene is commercially available. It was first prepared from tiglaldehyde via 2,3,4,5-tetramethylcyclopent-2-enone. Alternatively, 2-butenyllithium adds to ethyl acetate followed by acid-catalyzed dehydrocyclization: Organometallic derivatives Cp*H is a precursor to organometallic compounds containing the ligand, commonly called Cp*−. Some representative reactions leading to such Cp*–metal complexes follow: :Cp*H + C4H9Li → Cp*Li + C4H10 :Cp*Li + TiCl4 → Cp*TiCl3 + LiCl Some Cp* com ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organotungsten Chemistry
Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend to be more common. Mo(0) and more reduced states Molybdenum hexacarbonyl is the precursor to many substituted derivatives. It reacts with organolithium reagents to give anionic acyls which can be O-alkylated to give Fischer carbenes. 144px, Structure of (mesitylene)molybdenum tricarbonyl. Mo(CO)6 reacts with arenes to give piano-stool complexes such as (mesitylene)molybdenum tricarbonyl. Cycloheptatrienemolybdenum tricarbonyl, which is related to (arene)Mo(CO)3, reacts with trityl salts to give the cycloheptatrienyl complex: :(C7H8)Mo(CO)3 + (C6H5)3C+ → C7H7)Mo(CO)3sup>+ + (C6H5)3CH file:CHTMo(CO)3.png, 144px, Structure of Cycloheptatrienemolybdenum tricarbonyl. Reduction of Mo(CO)6 gives [Mo(CO)5]2− which is formally Mo(-II ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Pi Bond
In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbitals has an electron density of zero at a shared nodal plane that passes through the two bonded nuclei. This plane also is a nodal plane for the molecular orbital of the pi bond. Pi bonds can form in double and triple bonds but do not form in single bonds in most cases. The Greek letter π in their name refers to p orbitals, since the orbital symmetry of the pi bond is the same as that of the p orbital when seen down the bond axis. One common form of this sort of bonding involves p orbitals themselves, though d orbitals also engage in pi bonding. This latter mode forms part of the basis for metal-metal multiple bonding. Pi bonds are usually weaker than sigma bonds. The C-C double bond, composed of one sigma and one pi bond, has a bon ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Directed Ortho Metalation
Directed ortho metalation (DoM) is an adaptation of electrophilic aromatic substitution in which electrophiles attach themselves exclusively to the ortho- position of a direct metalation group or DMG through the intermediary of an aryllithium compound. The DMG interacts with lithium through a hetero atom. Examples of DMG's are the methoxy group, a tertiary amine group and an amide group.The compound can be produced by directed lithiation of anisole. The general principle is outlined in ''scheme 1''. An aromatic ring system with a DMG group 1 interacts with an alkyllithium such as ''n''-butyllithium in its specific aggregation state (hence (R-Li)n) to intermediate 2 since the hetero atom on the DMG is a Lewis base and lithium the Lewis acid. The very basic alkyllithium then deprotonates the ring in the nearest ortho- position forming the aryllithium 3 all the while maintaining the acid-base interaction. An electrophile reacts in the next phase in an electrophilic aromatic subs ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Fulvene
Fulvene (pentafulvene) is a hydrocarbon with the formula (CH=CH)2C=CH2. It is a prototype of a cross-conjugated hydrocarbon. Fulvene is rarely encountered, but substituted derivatives ( fulvenes) are numerous. They are mainly of interest as ligands and precursors to ligands in organometallic chemistry. See also *Fulvalene Fulvalene (bicyclopentadienylidene) is the member of the fulvalene family with the molecular formula C10H8. It is of theoretical interest as one of the simplest non-benzenoid conjugated hydrocarbons. Fulvalene is an unstable isomer of the mor ... * Methylenecyclopropene References {{Authority control Hydrocarbons Vinylidene compounds Cyclopentadienes ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organouranium Chemistry
Organouranium chemistry is the science exploring the properties, structure and reactivity of organouranium compounds, which are organometallic compounds containing a carbon to uranium chemical bond. The field is of some importance to the nuclear industry and of theoretical interest in organometallic chemistry. History The development of organouranium compounds started in World War II when the Manhattan Project required volatile uranium compounds for 235U/238U isotope separation. For example, Henry Gilman attempted to synthesize compounds like tetramethyluranium, and others worked on uranium metal carbonyls, but none of the efforts met success due to organouranium instability. After the discovery of ferrocene in 1951, Todd Reynolds and Geoffrey Wilkinson in 1956 synthesized the uranium metallocene Cp3UCl from sodium cyclopentadienide and uranium tetrachloride as a stable but extremely air-sensitive compound. In it, the U-Cl bond is an ionic bond, while the bonds with the three ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lewis Acid
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any species that has a filled orbital containing an electron pair which is not involved in bonding but may form a dative bond with a Lewis acid to form a Lewis adduct. For example, NH3 is a Lewis base, because it can donate its lone pair of electrons. Trimethylborane (Me3B) is a Lewis acid as it is capable of accepting a lone pair. In a Lewis adduct, the Lewis acid and base share an electron pair furnished by the Lewis base, forming a dative bond. In the context of a specific chemical reaction between NH3 and Me3B, a lone pair from NH3 will form a dative bond with the empty orbital of Me3B to form an adduct NH3•BMe3. The terminology refers to the contributions of Gilbert N. Lewis. From p. 142: "We are inclined to think of substances as po ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ziegler–Natta Catalyst
A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility: * Heterogeneous supported catalysts based on titanium compounds are used in polymerization reactions in combination with cocatalysts, organoaluminum compounds such as triethylaluminium, Al(C2H5)3. This class of catalyst dominates the industry. * Homogeneous catalysts usually based on complexes of the group 4 metals titanium, zirconium or hafnium. They are usually used in combination with a different organoaluminum cocatalyst, methylaluminoxane (or methylalumoxane, MAO). These catalysts traditionally contain metallocenes but also feature multidentate oxygen- and nitrogen-based ligands. Ziegler–Natta catalysts are used to polymerize terminal alkenes (ethylene and alkenes with the vinyl double bond): :''n'' CH2=CHR → − H2−CHRsub>' ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'', "gold-like" or "as gold"). It is a lustrous, grey-white, strong transition metal that closely resembles hafnium and, to a lesser extent, titanium. Zirconium is mainly used as a refractory and opacifier, although small amounts are used as an alloying agent for its strong resistance to corrosion. Zirconium forms a variety of inorganic and organometallic compounds such as zirconium dioxide and zirconocene dichloride, respectively. Five isotopes occur naturally, four of which are stable. Zirconium compounds have no known biological role. Characteristics Zirconium is a lustrous, greyish-white, soft, ductile, malleable metal that is solid at room temperature, though it is hard and brittle at lesser purities. In powder form, zirconium is highl ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
