A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5H−
5, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.
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, 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 representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.
Ferrocene is an organometallic compound with the formula Fe(C5H5)2. The molecule is a complex consisting of two cyclopentadienyl rings sandwiching 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 Fe(C5H5)+2. Ferrocene and the ferrocenium cation are sometimes abbreviated as Fc and Fc+ respectively.
A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups. Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (η5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring.
In chemistry, a (redox) non-innocent ligand is a ligand in a metal complex where the oxidation state is not clear. Typically, complexes containing non-innocent ligands are redox active at mild potentials. The concept assumes that redox reactions in metal complexes are either metal or ligand localized, which is a simplification, albeit a useful one.
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.
Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.
Rhodocene is a chemical compound with the formula [Rh(C5H5)2]. Each molecule contains an atom of rhodium bound between two planar aromatic systems of five carbon atoms known as cyclopentadienyl rings in a sandwich arrangement. It is an organometallic compound as it has (haptic) covalent rhodium–carbon bonds. The [Rh(C5H5)2] radical is found above 150 °C (302 °F) or when trapped by cooling to liquid nitrogen temperatures (−196 °C [−321 °F]). At room temperature, pairs of these radicals join via their cyclopentadienyl rings to form a dimer, a yellow solid.
Cyanometallates or cyanometalates are a class of coordination compounds, most often consisting only of cyanide ligands. Most are anions. Cyanide is a highly basic and small ligand, hence it readily saturates the coordination sphere of metal ions. The resulting cyanometallate anions are often used as building blocks for more complex structures called coordination polymers, the best known example of which is Prussian blue, a common dyestuff.
In polymer chemistry, chain walking (CW) or chain running or chain migration is a mechanism that operates during some alkene polymerization reactions. CW can be also considered as a specific case of intermolecular chain transfer. This reaction gives rise to branched and hyperbranched/dendritic hydrocarbon polymers. This process is also characterized by accurate control of polymer architecture and topology. The extent of CW, displayed in the number of branches formed and positions of branches on the polymers are controlled by the choice of a catalyst. The potential applications of polymers formed by this reaction are diverse, from drug delivery to phase transfer agents, nanomaterials, and catalysis.
In chemistry, compounds of palladium(III) feature the noble metal palladium in the unusual +3 oxidation state (in most of its compounds, palladium has the oxidation state II). Compounds of Pd(III) occur in mononuclear and dinuclear forms. Palladium(III) is most often invoked, not observed in mechanistic organometallic chemistry.
Parisa Mehrkhodavandi is a Canadian chemist and Professor of Chemistry at the University of British Columbia (UBC). Her research focuses on the design of new catalysts that can effect polymerization of sustainably sourced or biodegradable polymers.
A lanthanocene is a type of metallocene compound that contains an element from the lanthanide series. The most common lanthanocene complexes contain two cyclopentadienyl anions and an X type ligand, usually hydride or alkyl ligand.
β-Carbon elimination is a type of reaction in organometallic chemistry wherein an allyl ligand bonded to a metal center is broken into the corresponding metal-bonded alkyl (aryl) ligand and an alkene. It is a subgroup of elimination reactions. Though less common and less understood than β-hydride elimination, it is an important step involved in some olefin polymerization processes and transition-metal-catalyzed organic reactions.
Metal-ligand cooperativity (MLC) is a mode of reactivity in which a metal and ligand of a complex are both involved in the bond breaking or bond formation of a substrate during the course of a reaction. This ligand is an actor ligand rather than a spectator, and the reaction is generally only deemed to contain MLC if the actor ligand is doing more than leaving to provide an open coordination site. MLC is also referred to as "metal-ligand bifunctional catalysis." Note that MLC is not to be confused with cooperative binding.
Karsten Meyer is a German inorganic chemist and Chair of Inorganic and General Chemistry at the Friedrich-Alexander University of Erlangen-Nürnberg (FAU). His research involves the coordination chemistry of transition metals as well as uranium coordination chemistry, small molecule activation with these coordination complexes, and the synthesis of new chelating ligands. He is the 2017 recipient of the Elhuyar-Goldschmidt Award of the Spanish Royal Society of Chemistry, the Ludwig-Mond Award of the Royal Society of Chemistry, and the L.A. Chugaev Commemorative Medal of the Russian Academy of Sciences, among other awards. He also serves as an Associate Editor of the journal Organometallics since 2014.
Suzanne Cathleen Bart an American chemist who is a professor of inorganic chemistry at Purdue University. Her group's research focuses on actinide organometallic chemistry, and especially the characterization of low-valent organouranium complexes, actinide complexes with redox-active ligands, and discovery of new reactions that utilize these compounds. Bart's research has applications in the development of carbon-neutral fuel sources and the remediation of polluted sites.
In chemistry, a redox switch is a molecular device, which has two subunits, a functional component and a control component. The "control subunit" is redox-active, meaning that it can exist in either of two redox states. The "functional" component could have a variety of readouts, such as fluorescence, the binding of a substrate, or catalytic activity. The key feature of such redox switches is that the functional component is influenced by the control subunit. One of many examples of a redox switch consists of an anthracene substituent to a copper-thiacrown ether (14-ane-4) coordination complex. When in the cupric oxidation state, the anthracene does not fluoresce. When in the cuprous state, the assembly is highly fluorescent. Several redox switches have been produced from ferrocenecarboxylic acid, which can be conjugated to a number of functional components. 1,1'-Diaminoferrocene has been incorporated into various diamide and diimine ligands, which form catalysts that exhibit redox switching.
1,1'-Diaminoferrocene is the organoiron compound with the formula Fe(C5H4NH2)2. It is the simplest diamine derivative of ferrocene. It is a yellow, air-sensitive solid that is soluble in aqueous acid. The 1,1' part of its name refers to the location of the amine groups on separate rings. Compared to the parent ferrocene, the diamine is about 600 mV more reducing.
A molecular electron-reservoir complex is one of a class of redox-active systems which can store and transfer electrons stoichiometrically or catalytically without decomposition. The concept of electron-reservoir complexes was introduced by the work of French chemist, Didier Astruc. From Astruc's discoveries, a whole family of thermally stable, neutral, 19-electron iron(I) organometallic complexes were isolated and characterized, and found to have applications in redox catalysis and electrocatalysis. The following page is a reflection of the prototypal electron-reservoir complexes discovered by Didier Astruc.
