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Actinocene
Actinocenes are a family of organoactinide compounds consisting of metallocenes containing elements from the actinide series. They typically have a sandwich structure with two dianionic cyclooctatetraenyl ligands (COT2-, which is ) bound to an actinide-metal center (An) in the oxidation state IV, resulting in the general formula An(C8H8)2. Characterised actinocenes The most studied actinocene is uranocene, U(C8H8)2, which in 1968 was the first member of this family to be synthesised and is still viewed as the archetypal example. Other actinocenes that have been synthesised are protactinocene (Pa(C8H8)2), thorocene (Th(C8H8)2), neptunocene (Np(C8H8)2), and plutonocene (Pu(C8H8)2). Especially the latter two, neptunocene and plutonocene, have not been extensively studied experimentally since the 1980s because of the radiation hazard they pose. Bonding The actinide-cyclooctatetraenyl bonding has been of interest for multiple theoretical studies. Computational chemistry method ...
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Plutonocene
Plutonocene, Pu(C8H8)2, is an organoplutonium compound composed of a plutonium atom sandwiched between two cyclooctatetraenide (COT2-) rings. It is a dark red, very air-sensitive solid that is sparingly soluble in toluene and chlorocarbons. Plutonocene is a member of the actinocene family of metallocenes incorporating actinide elements in the +4 oxidation state. Compared to other actinocenes such as uranocene, plutonocene has been studied to a lesser degree since the 1980s due to the notable radiation hazard posed by the compound. Instead, it has mostly been the subject of theoretical studies relating to the bonding in the molecule. Structure and bonding The compound has been structurally characterised by single crystal XRD. The cyclooctatetraenide rings are eclipsed and assume a planar conformation with 8 equivalent C–C bonds of 1.41 Å length; the molecule possesses a centre of inversion at the position occupied by the plutonium atom. The Pu–COT distance (to the ring c ...
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Uranocene
Uranocene, U(C8H8)2, is an organouranium compound composed of a uranium atom sandwiched between two cyclooctatetraenide rings. It was one of the first organoactinide compounds to be synthesized. It is a green air-sensitive solid that dissolves in organic solvents. Uranocene, a member of the "actinocenes," a group of metallocenes incorporating elements from the actinide series. It is the most studied bis nnulene-metal system, although it has no known practical applications. Synthesis, structure and bonding Uranocene was first described in 1968 by the group of Andrew Streitwieser, when it was prepared by the reaction of dipotassium cyclooctatetraenide and uranium tetrachloride in THF at 0°C: : Uranocene is highly reactive toward oxygen, being pyrophoric in air but stable to hydrolysis. The x-ray crystal structure of uranocene was first elucidated by the group of Ken Raymond. Considering the molecule to be U4+(C8H82−)2, the η8- cyclooctatetraenide groups are planar, as ex ...
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Protactinium
Protactinium (formerly protoactinium) is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds in which protactinium is usually present in the oxidation state +5, but it can also assume +4 and even +3 or +2 states. Concentrations of protactinium in the Earth's crust are typically a few parts per trillion, but may reach up to a few parts per million in some uraninite ore deposits. Because of its scarcity, high radioactivity and high toxicity, there are currently no uses for protactinium outside scientific research, and for this purpose, protactinium is mostly extracted from spent nuclear fuel. The element was first identified in 1913 by Kazimierz Fajans and Oswald Helmuth Göhring and named ''brevium'' because of the short half-life of the specific isotope studied, i.e. protactinium-234. A more stable isotope of protactinium, 231Pa ...
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Neptunocene
Neptunocene, Np(C8H8)2, is an organoneptunium compound composed of a neptunium atom sandwiched between two cyclooctatetraenide (COT2-) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in chlorocarbons, in which it is sparingly soluble. The compound is quite air-sensitive. It was one of the first organoneptunium compounds to be synthesised, and is a member of the actinocene family of actinide-based metallocenes. Structure The sandwich structure of neptunocene has been determined by single crystal XRD. The COT2- rings are found to be planar with 8 equivalent C–C bonds of 1.385 Å length, and sit parallel in an eclipsed conformation. The Np–COT distance (to the ring centroid) is 1.909 Å and the individual Np–C distances are 2.630 Å. Neptunocene assumes a monoclinic crystal structure (''P''21/''n'' space group) which is isomorphous to uranocene and thorocene but not to plutonocene. Synthesis and properties Neptunocene was first syn ...
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Cyclooctatetraenide Anion
In chemistry, the cyclooctatetraenide anion or cyclooctatetraenide, more precisely cyclooctatetraenediide, is an aromatic species with a formula of 8H8sup>2− and abbreviated as COT2−. It is the dianion of cyclooctatetraene. Salts of the cyclooctatetraenide anion can be stable, e.g., Dipotassium cyclooctatetraenide or disodium cyclooctatetraenide. More complex coordination compounds are known as cyclooctatetraenide complexes, such as the actinocenes. The structure is a planar symmetric octagon stabilized by resonance, meaning each atom bears a charge of −. The length of the bond between carbon atoms is 1.432 Å. There are 10 π electrons. The structure can serve as a ligand with various metals. List of salts See also *Tropylium ion *Cyclopentadienyl anion In chemistry, the cyclopentadienyl anion or cyclopentadienide is an aromatic species with a formula of and abbreviated as Cp−. It is formed from the deprotonation of the molecule cyclopentadi ...
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Metallocene
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. ...
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Sandwich Compound
In organometallic chemistry, a sandwich compound is a chemical compound featuring a metal bound by haptic, covalent bonds to two arene (ring) ligands. The arenes have the formula , substituted derivatives (for example ) and heterocyclic derivatives (for example ). Because the metal is usually situated between the two rings, it is said to be "sandwiched". A special class of sandwich complexes are the metallocenes. The term ''sandwich compound'' was introduced in organometallic nomenclature in 1956 in a report by J. D. Dunitz, L. E. Orgel and R. A. Rich, who confirmed the structure of ferrocene by X-ray crystallography. The correct structure, in which the molecule features an iron atom ''sandwiched'' between two parallel cyclopentadienyl rings, had been proposed several years previously by Robert Burns Woodward and, separately, by Ernst Otto Fischer. The structure helped explain puzzles about ferrocene's conformers. This result further demonstrated the power ...
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Organoactinide
Organoactinide chemistry is the science exploring the properties, structure and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond. Like most organometallic compounds, the organoactinides are air sensitive and need to be handled using the appropriate methods. Organometallic complexes with σ-bonding Most common organoactinide complexes involve π-bonding with ligands such as cyclopentadienyl, but there are a few exceptions with σ-bonding, namely in thorium and uranium chemistry as these are the most easily handleable elements of this group. Alkyl and aryl compounds Attempts to synthesize uranium alkyls were first made during the Manhattan project by Henry Gilman, inspired by the volatility of main group organometallics. However he noticed that these compounds tend to be highly unstable. Marks and Seyam attempted to synthesize them from UCl using organolithium reagents, but these decomposed quickl ...
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Organoactinide Chemistry
Organoactinide chemistry is the science exploring the properties, structure and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond. Like most organometallic compounds, the organoactinides are air sensitive and need to be handled using the appropriate methods. Organometallic complexes with σ-bonding Most common organoactinide complexes involve π-bonding with ligands such as cyclopentadienyl, but there are a few exceptions with σ-bonding, namely in thorium and uranium chemistry as these are the most easily handleable elements of this group. Alkyl and aryl compounds Attempts to synthesize uranium alkyls were first made during the Manhattan project by Henry Gilman, inspired by the volatility of main group organometallics. However he noticed that these compounds tend to be highly unstable. Marks and Seyam attempted to synthesize them from UCl using organolithium reagents, but these decomposed quickly. ...
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Neodymium
Neodymium is a chemical element with the symbol Nd and atomic number 60. It is the fourth member of the lanthanide series and is considered to be one of the rare-earth metals. It is a hard, slightly malleable, silvery metal that quickly tarnishes in air and moisture. When oxidized, neodymium reacts quickly producing pink, purple/blue and yellow compounds in the +2, +3 and +4 oxidation states. It is generally regarded as having one of the most complex spectra of the elements. Neodymium was discovered in 1885 by the Austrian chemist Carl Auer von Welsbach, who also discovered praseodymium. It is present in significant quantities in the minerals monazite and bastnäsite. Neodymium is not found naturally in metallic form or unmixed with other lanthanides, and it is usually refined for general use. Neodymium is fairly common—about as common as cobalt, nickel, or copper—and is widely distributed in the Earth's crust. Most of the world's commercial neodymium is mined in China, as ...
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Lanthanide
The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttrium, are often collectively known as the rare-earth elements or rare-earth metals. The informal chemical symbol Ln is used in general discussions of lanthanide chemistry to refer to any lanthanide. All but one of the lanthanides are f-block elements, corresponding to the filling of the 4f electron shell. There is some dispute on whether lanthanum or lutetium is a d-block element, but lutetium is usually considered so by those who study the matter; it is included due to its chemical similarities with the other 14. All lanthanide elements form trivalent cations, Ln3+, whose chemistry is largely determined by the ionic radius, which decreases steadily from lanthanum to lutetium. These elements are called lanthanides because the ele ...
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Chemical Bond
A chemical bond is a lasting attraction between atoms or ions that enables the formation of molecules and crystals. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds, or through the sharing of electrons as in covalent bonds. The strength of chemical bonds varies considerably; there are "strong bonds" or "primary bonds" such as covalent, ionic and metallic bonds, and "weak bonds" or "secondary bonds" such as dipole–dipole interactions, the London dispersion force and hydrogen bonding. Strong chemical bonding arises from the sharing or transfer of electrons between the participating atoms. Since opposite electric charges attract, the negatively charged electrons surrounding the nucleus and the positively charged protons within a nucleus attract each other. An electron positioned between two nuclei will be attracted to both of them, and the nuclei will be attracted toward electrons in this position. This attraction const ...
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