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Titanocene
Titanocene dichloride is the organotitanium compound with the formula ( ''η''5-C5H5)2TiCl2, commonly abbreviated as Cp2TiCl2. This metallocene is a common reagent in organometallic and organic synthesis. It exists as a bright red solid that slowly hydrolyzes in air. It shows antitumour activity and was the first non-platinum complex to undergo clinical trials as a chemotherapy drug. Preparation and structure The standard preparations of Cp2TiCl2 start with titanium tetrachloride. The original synthesis by Wilkinson and Birmingham, using sodium cyclopentadienide, is still commonly used: :2 NaC5H5 + TiCl4 → (C5H5)2TiCl2 + 2 NaCl It can also be prepared by using freshly distilled cyclopentadiene rather than its sodium derivative: :2 C5H6 + TiCl4 → (C5H5)2TiCl2 + 2 HCl Focusing on the geometry of the Ti center, Cp2TiCl2 adopts a distorted tetrahedral geometry (counting Cp as a monodentate ligand). The Ti-Cl distance is 2.37 Å and the Cl-Ti-Cl angle is ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organotitanium Compound
Organotitanium chemistry is the science of organotitanium compounds describing their physical properties, synthesis, and reactions. Organotitanium compounds in organometallic chemistry contain carbon-titanium chemical bonds. They are reagents in organic chemistry and are involved in major industrial processes. Brief history Although the first attempt to prepare an organotitanium compound dates back to 1861, the first example was not reported until 1954. In that year titanocene dichloride was described by Wilkinson and Birmingham. Independently, titanium-based Ziegler–Natta catalysts were described leading to major commercial applications, for which the 1963 Nobel Prize in Chemistry was awarded. This technology underscored the technical significance of organotitanium chemistry. Properties The titanium electron configuration ( rd24s2) vaguely resembles that of carbon and like carbon, the +4 oxidation state dominates. Titanium is however a much larger element than carbon, reflected ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Titanocene Pentasulfide
Titanocene pentasulfide is the organotitanium compound with the formula (C5H5)2TiS5, commonly abbreviated as Cp2TiS5. This metallocene exists as a bright red solid that is soluble in organic solvents. It is of academic interest as a precursor to unusual allotropes of elemental sulfur as well as some related inorganic rings. Preparation and structure Titanocene pentasulfide is prepared by treating Cp2TiCl2 with polysulfide salts: It was first produced by the addition of elemental sulfur to titanocene dicarbonyl: :(C5H5)2Ti(CO)2 + S8 → (C5H5)2TiS5 + 2 CO The complex is viewed as a pseudotetrahedral complex of Ti(IV). The Ti–S distances are 2.420 and 2.446 Å and the S–S bond distances are of a normal range, 2.051–2.059 Å. The molecule exhibits a dynamic NMR spectrum owing to the chair–chair equilibrium of the TiS5 ring which equivalizes the Cp signals at high temperatures. Reactions Cp2TiS5 reacts with sulfur and selenium chlorides, E''x''Cl2, to ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Petasis Reagent
The Petasis reagent, named after Nicos A. Petasis, is an organotitanium compound with the formula Cp2Ti(CH3)2. It is an orange-colored solid. Preparation and use The Petasis reagent is prepared by the salt metathesis reaction of methylmagnesium chloride or methyllithium with titanocene dichloride: : Cp2TiCl2 + 2 CH3MgCl → Cp2Ti(CH3)2 + 2 MgCl2 This compound is used for the transformation of carbonyl groups to terminal alkenes. It exhibits similar reactivity to the Tebbe reagent and Wittig reaction. Unlike the Wittig reaction, the Petasis reagent can react with a wide range of aldehydes, ketones and esters. The Petasis reagent is also very air stable, and is commonly used in solution with toluene or THF. The Tebbe reagent and the Petasis reagent share a similar reaction mechanism. The active olefinating reagent, Cp2TiCH2, is generated in situ upon heating. With the organic carbonyl, this titanium carbene forms a four membered oxatitanacyclobutane that releases the te ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tebbe Reagent
Tebbe's reagent is the organometallic compound with the formula (C5H5)2TiCH2ClAl(CH3)2. It is used in the methylenation of carbonyl compounds, that is it converts organic compounds containing the R2C=O group into the related R2C=CH2 derivative. It is a red solid that is pyrophoric in the air, and thus is typically handled with air-free techniques. It was originally synthesized by Fred Tebbe at DuPont Central Research. Tebbe's reagent contains two tetrahedral metal centers linked by a pair of bridging ligands. The titanium has two cyclopentadienyl (, or Cp) rings and aluminium has two methyl groups. The titanium and aluminium atoms are linked together by both a methylene bridge (-CH2-) and a chloride atom in a nearly square-planar (Ti–CH2–Al–Cl) geometry. The Tebbe reagent was the first reported compound where a methylene bridge connects a transition metal (Ti) and a main group metal (Al).Herrmann, W.A., "The Methylene Bridge" ''Advances in Organometallic Chemistry'' 1982, ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Titanium Tetrachloride
Titanium tetrachloride is the inorganic compound with the formula . It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide () and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula () to the word. Properties and structure is a dense, colourless distillable liquid, although crude samples may be yellow or even red-brown. It is one of the rare transition metal halides that is a liquid at room temperature, being another example. This property reflects the fact that molecules of weakly self-associate. Most metal chlorides are polymers, wherein the chloride atoms bridge between the metals. Its melting and boiling points are similar to those of . has a "closed" electronic shell, with the same numbe ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Vanadocene Dichloride
Vanadocene dichloride is an organometallic complex with formula ( ''η''5- C5H5)2VCl2 (commonly abbreviated as Cp2VCl2). It is a structural analogue of titanocene dichloride but with vanadium(IV) instead of titanium(IV). This compound has one unpaired electron, hence Cp2VCl2 is paramagnetic. Vanadocene dichloride is a suitable precursor for variety of bis(cyclopentadienyl)vanadium(IV) compounds. Preparation Cp2VCl2 was first prepared by Wilkinson and Birmingham via the reaction of NaC5H5 and VCl4 in THF. Reactions and use The compound has been used in organic synthesis. Reduction of vanadocene dichloride gives vanadocene, (C5H5)2V. Like titanocene dichloride, this organovanadium compound was investigated as a potential anticancer drug. It was conjectured to function by interactions with the protein transferrin Transferrins are glycoproteins found in vertebrates which bind to and consequently mediate the transport of iron (Fe) through blood plasma. They are produced in the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Polysulfide
Polysulfides are a class of chemical compounds containing chains of sulfur atoms. There are two main classes of polysulfides: inorganic and organic. Among the inorganic polysulfides, there are ones which contain anions, which have the general formula . These anions are the conjugate bases of the hydrogen polysulfides . Organic polysulfides generally have the formulae , where R = alkyl or aryl. Polysulfide salts and complexes The alkali metal polysulfides arise by treatment of a solution of sulfide, e.g. sodium sulfide, with elemental sulfur: : In some cases, these anions have been obtained as organic salts, which are soluble in organic solvents. The energy released in the reaction of sodium and elemental sulfur is the basis of battery technology. The sodium–sulfur battery and the lithium–sulfur battery require high temperatures to maintain liquid polysulfide and -conductive membranes that are unreactive toward sodium, sulfur, and sodium sulfide. Polysulfides are ligands i ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hapticity
In coordination chemistry, hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms. The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η2 describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated (otherwise the κ-notation is used). In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity (not hapticity), and the κ-notation is used once again. When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands. History The need for additional nomenclature for organometallic compounds became apparent in the mid-1950s when Dunitz, Orgel, and Rich described the structure of the "sandwich complex" ferrocene by X-ray crystallography where an iron atom is ''"sandwiched"'' between two parallel cyclopen ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
(Cyclopentadienyl)titanium Trichloride
(Cyclopentadienyl)titanium trichloride is an organotitanium compound with the formula (CH)TiCl. It is a moisture sensitive orange solid. The compound adopts a piano stool geometry. Preparation and reactions (CH)TiCl is prepared by the reaction of titanocene dichloride and titanium tetrachloride Titanium tetrachloride is the inorganic compound with the formula . It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. is a volatile liquid. Upon contact with humid air, it forms thick clouds ...: :(CH)TiCl + TiCl → 2 (CH)TiCl The complex is electrophilic, readily forming alkoxide complexes upon treatment with alcohols. Reduction of (cyclopentadienyl)titanium trichloride with zinc powder gives the polymeric Ti(III) derivative (cyclopentadienyl)titanium dichloride: :(CH)TiCl + 0.5Zn → 1/n CH)TiCl + 0.5ZnCl See also * (Cyclopentadienyl)zirconium trichloride * (Pentamethylclopentadienyl)titanium trichloride * (Inden ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Niobocene Dichloride
Niobocene dichloride is the organometallic compound with the formula (C5H5)2NbCl2, abbreviated Cp2NbCl2. This paramagnetic brown solid is a starting reagent for the synthesis of other organoniobium compounds. The compound adopts a pseudotetrahedral structure with two cyclopentadienyl and two chloride substituents attached to the metal. A variety of similar compounds are known, including Cp2TiCl2. Preparation and structure It was originally reported by Geoffrey Wilkinson. It is prepared via a multistep reaction beginning with treatment of niobium pentachloride with cyclopentadienylsodium: :NbCl5 + 6 NaC5H5 → 5 NaCl + (C5H5)4Nb + organic products :(C5H5)4Nb + 2 HCl + 0.5 O2 → 2O.html" ;"title="sub>2O">sub>2Ol2 + 2 C5H6 :2 HCl + 2O.html" ;"title="sub>2O">sub>2Ol2 + SnCl2 → 2 (C5H5)2NbCl2 + SnCl4 + H2O The compound adopts a "clamshell" structure characteristic of a bent metallocene where the Cp rings are not parallel, the average Cp(centroi ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Molybdocene Dichloride
Molybdocene dichloride is the organomolybdenum compound with the formula ( η5-C5H5)2MoCl2 and IUPAC name dichlorobis(η5-cyclopentadienyl)molybdenum(IV), and is commonly abbreviated as Cp2MoCl2. It is a brownish-green air- and moisture-sensitive powder. In the research laboratory, it is used to prepare many derivatives. Preparation and structure The compound is prepared from molybdocene dihydride by treatment with chloroform: :(C5H5)2MoH2 + 2 CHCl3 → (C5H5)2MoCl2 + 2 CH2Cl2 The compound adopts a "clamshell" structure where the Cp rings are not parallel, the average Cp(centroid)-M-Cp angle being 130.6°. The two chloride ligands are cis, the Cl-Mo-Cl angle of 82° being narrower than in niobocene dichloride (85.6°), which in turn is less than in zirconacene dichloride Zirconocene dichloride is an organozirconium compound composed of a zirconium central atom, with two cyclopentadienyl and two chloro ligands. It is a colourless diamagnetic solid that is somewhat stable in air ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
