Cyclopentadienyl Complex
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Cyclopentadienyl Complex
A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups (, abbreviated as Cp−). Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (''η''5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring.Elschenbroich, C. "Organometallics" (2006) Wiley-VCH: Weinheim. Examples ''Bis''cyclopentadienyl complexes are called metallocenes. A famous example of this type of complex is ferrocene (FeCp2), which has many analogues for other metals, such as chromocene (CrCp2), cobaltocene (CoCp2), and nickelocene (NiCp2). When the Cp rings are mutually parallel the compound is known as a sandwich complex. This area of organometallic chemistry was first developed in the 1950s. Bent metallocenes are represented by compounds of the type Cp2Lx Some are catalysts for ethylene polymerization. Metallocenes are often thermally stable, and find use as cata ...
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Methylcyclopentadienylmanganese Tricarbonyl
Methylcyclopentadienyl manganese tricarbonyl (MMT or MCMT) is an organomanganese compound with the formula (C5H4CH3)Mn(CO)3. Initially marketed as a supplement for use in leaded gasoline, MMT was later used in unleaded gasoline to increase the octane rating. Following the implementation of the Clean Air Act (United States) (CAA) in 1970, MMT continued to be used alongside tetraethyl lead (TEL) in the US as leaded gasoline was phased out (prior to TEL finally being banned from US gasoline in 1995), and was also used in unleaded gasoline until 1977. Ethyl Corporation obtained a waiver from the U.S. EPA (Environmental Protection Agency) in 1995, which allows the use of MMT in US unleaded gasoline (not including reformulated gasoline) at a treat rate equivalent to 8.3 mg Mn/L (manganese per liter). MMT has been used in Canadian gasoline since 1976 (and in numerous other countries for many years) at a concentration up to 8.3 mg Mn/L (though the importation and inter ...
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Decamethylcobaltocene
Decamethylcobaltocene is an organocobalt compound with the formula Co(C5(CH3)5)2, abbreviated CoCp{{su, p=∗, b=2. It is a dark brown solid. This compound is used as a strong reducing agent in organometallic chemistry. Synthesis Decamethylcobaltocene is prepared by treatment of LiCp* with CoCl2: :2 LiCp* + CoCl2 → 2 LiCl + CoCp*2 The permethylated form is more air-sensitive than the parent cobaltocene, owing to the inductive effects of methyl groups. It is a thermally stable compound and undergoes vacuum sublimation. Bonding Co(C5Me5)2 is a metallocene, having idealized D5d symmetry. Like cobaltocene, decamethylcobaltocene has a 19 electron count in its valence shell and is paramagnetic. It is used as a one-electron reducing agent. Relative to the ferrocene/ferrocenium couple, the redox potential for the oCp*2sup>+/0 couple is -1.94 V compared to the oCp2sup>+/0 couple of -1.33 V (in dichloromethane). For comparison, the difference between the redox ferrocen ...
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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 electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical areas, including bioinorganic and medicinal chemistry, homogeneous catalysis, and environmental chemi ...
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Base (chemistry)
In chemistry, there are three definitions in common use of the word base, known as Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century. In 1884, Svante Arrhenius proposed that a base is a substance which dissociates in aqueous solution to form Hydroxide ions OH−. These ions can react with hydrogen ions (H+ according to Arrhenius) from the dissociation of acids to form water in an acid–base reaction An acid–base reaction is a chemical reaction that occurs between an acid and a base. It can be used to determine pH via titration. Several theoretical frameworks provide alternative conceptions of the reaction mechanisms and their applica .... A base was therefore a metal hydroxide such as Sodium hydroxide, NaOH or Calcium hydroxide, Ca(OH)2. Such aqueous hydroxide solutions were also described by certain characteristic properties. ...
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Cyclopentadiene
Cyclopentadiene is an organic compound with the chemical formula, formula C5H6.LeRoy H. Scharpen and Victor W. Laurie (1965): "Structure of cyclopentadiene". ''The Journal of Chemical Physics'', volume 43, issue 8, pages 2765-2766. It is often abbreviated CpH because the cyclopentadienyl anion is abbreviated Cp−. This colorless liquid has a strong and unpleasant odor. At room temperature, this cyclic diene dimer (chemistry), dimerizes over the course of hours to give dicyclopentadiene via a Diels–Alder reaction. This dimer can be retro-Diels–Alder reaction, restored by heating to give the monomer. The compound is mainly used for the production of cyclopentene and its derivatives. It is popularly used as a precursor to the cyclopentadienyl anion (Cp−), an important ligand in cyclopentadienyl complexes in organometallic chemistry. Production and reactions Cyclopentadiene production is usually not distinguished from dicyclopentadiene since they interconvert. They ...
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Cyclopentadienylthallium
Cyclopentadienylthallium, also known as thallium cyclopentadienide, is an organothallium compound with formula C5H5Tl. This light yellow solid is insoluble in most organic solvents, but sublimes readily. It is used as a precursor to transition metal and main group cyclopentadienyl complexes, as well as organic cyclopentadiene derivatives. Preparation and structure Cyclopentadienylthallium is prepared by the reaction of thallium(I) sulfate, sodium hydroxide, and cyclopentadiene: : Tl2SO4 + 2 NaOH → 2 TlOH + Na2SO4 : TlOH + C5H6 → TlC5H5 + H2O The compound adopts a polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...ic structure, consisting of infinite chains of bent metallocenes. The Tl---Tl---Tl angles are 130°.Falk Olbrich, Ulrich Behrens "Crystal structure of caten ...
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Trimethylsilylcyclopentadiene
Trimethylsilyl cyclopentadiene is an organosilicon compound with the chemical formula C5H5Si(CH3)3. It exists as a colorless liquid. It is used in the synthesis of some metal cyclopentadienyl complexes and has attracted interest for its fluxional structure. Trimethylsilyl cyclopentadiene is an example of a molecule that undergoes rapid sigmatropic rearrangement. Observations of trimethylsilyl cyclopentadiene using gas phase NMR spectroscopy show that the protons on the ring are chemically equivalent, indicated by a single peak. This phenomenon, an example of fluxionality, is explained by the migration of the silyl group from carbon-to-carbon, thereby giving the appearance of equivalent CH signals. Properties: refractive index ''n''20/D 1.471(lit.) bp 138-140 °C(lit.) density 0.833 g/mL at 25 °C(lit.) storage temp. −20 °C Synthesis Trimethylsilyl cyclopentadiene is prepared by the reaction trimethylsilyl chloride ...
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Lithium Cyclopentadienide
Lithium cyclopentadienide is an organolithium compound with the formula C5H5Li. The compound is often abbreviated as LiCp, where Cp− is the cyclopentadienide anion. Lithium cyclopentadienide is a colorless solid, although samples often are pink owing to traces of oxidized impurities. Preparation, structure and reactions Lithium cyclopentadienide is commercially available as a solution in THF. It is prepared by treating cyclopentadiene with butyllithium: :C5H6 + LiC4H9 → LiC5H5 + C4H10 Because lithium cyclopentadienide is usually handled as a solution, the solvent-free solid is rarely encountered. According to X-ray crystallography, LiCp is a "polydecker" sandwich complex, consisting of an infinite chain of alternating Li+ centers sandwiched between ''μ''- ''η''5:''η''5-C5H5 ligands. In the presence of amines or ethers, LiCp gives adducts, e.g. (''η''5-Cp)Li(TMEDA). LiCp is a common reagent for the preparation of cyclopentadienyl complexes. See also *Sodium cy ...
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Salt Metathesis Reaction
A salt metathesis reaction, sometimes called a double displacement reaction, is a chemical process involving the exchange of bonds between two reacting chemical species which results in the creation of products with similar or identical bonding affiliations. This reaction is represented by the general scheme: :AB + CD -> AD + CB The bond between the reacting species can be either ionic or covalent. Classically, these reactions result in the precipitation of one product. In older literature, the term double decomposition is frequently encountered. The term double decomposition is more specifically used when at least one of the substances does not dissolve in the solvent, as the ligand or ion exchange takes place in the solid state of the reactant. For example: :AX(aq) + BY(s) → AY(aq) + BX(s). Types of reactions Counterion exchange Salt metathesis is a common technique for exchanging counterions. The choice of reactants is guided by a solubility chart or lattice energy. ...
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Indenyl Effect
In organometallic chemistry, a transition metal indenyl complex is a coordination compound that contains one or more indenyl ligands. The indenyl ligand is formally the anion derived from deprotonation of indene. The η5-indenyl ligand is related to the η5cyclopentadienyl anion (Cp), thus indenyl analogues of many cyclopentadienyl complexes are known. Indenyl ligands lack the 5-fold symmetry of Cp, so they exhibit more complicated geometries. Furthermore, some indenyl complexes also exist with only η3-bonding mode. The η5- and η3-bonding modes sometimes interconvert. Preparation and structure Indene is deprotonated by butyl lithium and related reagents to give the equivalent of the indenyl anion: :C9H8 + BuLi → LiC9H7 + BuH The resulting lithium indenide can be used to prepare indenyl complexes by salt metathesis reactions of metal halides. When the metal halide is easily reduced, the trimethylstannylindenyl can be used as a source of indenyl anion: :Me3SnC9H7 + ...
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Allyl Ligand
Transition-metal allyl complexes are coordination complexes with allyl and its derivatives as ligands. Allyl is the radical with the connectivity CH2CHCH2, although as a ligand it is usually viewed as an allyl anion CH2=CH−CH2−, which is usually described as two equivalent resonance structures. Examples The allyl ligand is commonly found in organometallic chemistry. Most commonly, allyl ligands bind to metals via all three carbon atoms, the η3-binding mode. The η3-allyl group is classified as an LX-type ligand in the Green LXZ ligand classification scheme, serving as a 3e– donor using neutral electron counting and 4e– donor using ionic electron counting. More common are complexes with allyl and other ligands. Examples include (η3-allyl)Mn(CO)4 and CpPd(allyl). Homoleptic complexes * bis(allyl)nickel * bis(allyl)palladium * bis(allyl)platinum *tris(allyl)chromium * tris(allyl)rhodium * tris(allyl)iridium Synthetic methods Allyl complexes are often generated by ox ...
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