Decamethylcobaltocene
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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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Cobaltocene
Cobaltocene, known also as bis(cyclopentadienyl)cobalt(II) or even "bis Cp cobalt", is an organocobalt compound with the formula Co(C5H5)2. It is a dark purple solid that sublimes readily slightly above room temperature. Cobaltocene was discovered shortly after ferrocene, the first metallocene. Due to the ease with which it reacts with oxygen, the compound must be handled and stored using air-free techniques. Synthesis Cobaltocene is prepared by the reaction of sodium cyclopentadienide (NaC5H5) with anhydrous cobalt(II) chloride in THF solution. Sodium chloride is cogenerated, and the organometallic product is usually purified by vacuum sublimation. Structure and bonding In Co(C5H5)2 the Co centre is "sandwiched" between two cyclopentadienyl (Cp) rings. The Co–C bond lengths are about 2.1 Å, slightly longer than the Fe–C bond in ferrocene. Co(C5H5)2 belongs to a group of organometallic compounds called metallocenes or sandwich compounds. Cobaltocene has 19 valence ...
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Organocobalt Compound
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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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 ...
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Sublimation (phase Transition)
Sublimation is the transition of a substance directly from the solid to the gas state, without passing through the liquid state. Sublimation is an endothermic process that occurs at temperatures and pressures below a substance's triple point in its phase diagram, which corresponds to the lowest pressure at which the substance can exist as a liquid. The reverse process of sublimation is deposition or desublimation, in which a substance passes directly from a gas to a solid phase. Sublimation has also been used as a generic term to describe a solid-to-gas transition (sublimation) followed by a gas-to-solid transition ( deposition). While vaporization from liquid to gas occurs as evaporation from the surface if it occurs below the boiling point of the liquid, and as boiling with formation of bubbles in the interior of the liquid if it occurs at the boiling point, there is no such distinction for the solid-to-gas transition which always occurs as sublimation from the surface. At ...
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Metallocene
A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metallic element, metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride, vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalysis, catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze Ziegler–Natta catalyst, olefin polymerization. Some metallocenes consist of metal plus two cyclooctatetraenide anions (, abbreviated cot2−), namely the lanthanocenes and the actinocenes (uranocene and others). Metallocenes are a subset of a broader class of compounds called sandwich compounds. In the structure shown at right, the two pentagons are the cyclopentadienyl anions with circles inside them indicating they are aromaticity, aromatically st ...
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Reducing Agent
In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth metals, formic acid, oxalic acid, and sulfite compounds. In their pre-reaction states, reducers have extra electrons (that is, they are by themselves reduced) and oxidizers lack electrons (that is, they are by themselves oxidized). This is commonly expressed in terms of their oxidation states. An agent's oxidation state describes its degree of loss of electrons, where the higher the oxidation state then the fewer electrons it has. So initially, prior to the reaction, a reducing agent is typically in one of its lower possible oxidation states; its oxidation state increases during the reaction while that of the oxidizer decreases. Thus in a redox reaction, the agent whose oxidation state increases, that "loses/Electron donor, donates electrons ...
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Ferrocene
Ferrocene is an organometallic compound with the formula . The molecule is a complex consisting of two cyclopentadienyl rings bound to a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation . The rapid growth of organometallic chemistry is often attributed to the excitement arising from the discovery of ferrocene and its many analogues, such as metallocenes. History Discovery Ferrocene was discovered by accident thrice. The first known synthesis may have been made in the late 1940s by unknown researchers at Union Carbide, who tried to pass hot cyclopentadiene vapor through an iron pipe. The vapor reacted with the pipe wall, creating a "yellow sludg ...
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Ferrocenium
Ferrocenium tetrafluoroborate is an organometallic compound with the formula e(C5H5)2F4. This salt is composed of the cation e(C5H5)2sup>+ and the tetrafluoroborate anion (). The related hexafluorophosphate is also a popular reagent with similar properties. The cation is often abbreviated Fc+ or Cp2Fe+. The salt is deep blue in color and paramagnetic. Ferrocenium salts are sometimes used as one-electron oxidizing agents, and the reduced product, ferrocene, is inert and readily separated from ionic products. The ferrocene–ferrocenium couple is often used as a reference in electrochemistry. The standard potential of ferrocene-ferrocenium is 0.400 V vs. the normal hydrogen electrode (NHE) and is often assumed to be invariant between different solvents. Preparation Commercially available, this compound may be prepared by oxidizing ferrocene typically with ferric salts followed by addition of fluoroboric acid. A variety of other oxidants work well also, such as nitrosyl tetr ...
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Dichloromethane
Dichloromethane (DCM or methylene chloride, methylene bichloride) is an organochlorine compound with the formula . This colorless, volatile liquid with a chloroform-like, sweet odour is widely used as a solvent. Although it is not miscible with water, it is slightly polar, and miscible with many organic solvents.Rossberg, M. ''et al.'' (2006) "Chlorinated Hydrocarbons" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. . Occurrence Natural sources of dichloromethane include oceanic sources, macroalgae, wetlands, and volcanoes. However, the majority of dichloromethane in the environment is the result of industrial emissions. Production DCM is produced by treating either chloromethane or methane with chlorine gas at 400–500 °C. At these temperatures, both methane and chloromethane undergo a series of reactions producing progressively more chlorinated products. In this way, an estimated 400,000 tons were produced in the US, Europe, and Japan in 1993. ...
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Decamethylferrocene
Decamethylferrocene or bis(pentamethylcyclopentadienyl)iron(II) is a chemical compound with formula or . It is a sandwich compound, whose molecule has an iron(II) cation attached by coordination bonds between two pentamethylcyclopentadienyl anions (, ). It can also be viewed as a derivative of ferrocene, with a methyl group replacing each hydrogen atom of its cyclopentadienyl rings. The name and formula are often abbreviated to DmFc, or . This compound is a yellow crystalline solid that is used in chemical laboratories as a weak reductant. The iron(II) core is easily oxidized to iron(III), yielding the monovalent cation decamethylferrocenium, and even to higher oxidation states. Preparation Decamethylferrocene is prepared in the same manner as ferrocene from pentamethylcyclopentadiene. This method can be used to produce other decamethylcyclopentadienyl sandwich compounds. :2 Li(C5Me5) + FeCl2 → Fe(C5Me5)2 + 2 LiCl The product can be purified by sublimation. has stagg ...
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Organocobalt Compounds
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 c ...
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Metallocenes
A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride, vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to p2ZrCH3sup>+ catalyze olefin polymerization. Some metallocenes consist of metal plus two cyclooctatetraenide anions (, abbreviated cot2−), namely the lanthanocenes and the actinocenes (uranocene and others). Metallocenes are a subset of a broader class of compounds called sandwich compounds. In the structure shown at right, the two pentagons are the cyclopentadienyl anions with circles inside them indicating they are aromatically stabilized. Here they are shown in a staggered conformation. Hist ...
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