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Sigma-bond Metathesis
In organometallic chemistry, sigma-bond metathesis is a chemical reaction wherein a metal-ligand sigma bond undergoes metathesis (exchange of parts) with the sigma bond in some reagent. The reaction is illustrated by the exchange of lutetium(III) methyl complex with a hydrocarbon (R-H): :(C5Me5)2Lu-CH3 + R-H → (C5Me5)2Lu-R + CH4 This reactivity was first observed by Patricia Watson, a researcher at duPont.{{cite journal, author=Watson, Patricia, title=Methane exchange reactions of lanthanide and early-transition-metal methyl complexes, journal=Journal of the American Chemical Society, year=1983, volume=32, pages=6491–6493, doi=10.1021/ja00359a023 The reaction is mainly observed for complexes of metals with d0 configuration, e.g. complexes of Sc(III), Zr(IV), Nb(IV), Ta(V), etc. f-Element complexes also participate, regardless of the number of f-electrons. The reaction is thought to proceed via cycloaddition. Indeed, the rate of the reaction is characterized by a highly ...
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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 r ...
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Chemical Reaction
A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the Atomic nucleus, nuclei (no change to the elements present), and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive Chemical element, elements where both electronic and nuclear changes can occur. The substance (or substances) initially involved in a chemical reaction are called reagent, reactants or reagents. Chemical reactions are usually characterized by a chemical change, and they yield one or more Product (chemistry), products, which usually have properties different from the reactants. Reactions often consist of a sequence o ...
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Sigma Bond
In chemistry, sigma bonds (σ bonds) are the strongest type of covalent chemical bond. They are formed by head-on overlapping between atomic orbitals. Sigma bonding is most simply defined for diatomic molecules using the language and tools of symmetry groups. In this formal approach, a σ-bond is symmetrical with respect to rotation about the bond axis. By this definition, common forms of sigma bonds are s+s, pz+pz, s+pz and dz2+dz2 (where z is defined as the axis of the bond or the internuclear axis). Quantum theory also indicates that molecular orbitals (MO) of identical symmetry actually mix or ''hybridize''. As a practical consequence of this mixing of diatomic molecules, the wavefunctions s+s and pz+pz molecular orbitals become blended. The extent of this mixing (or hybridization or blending) depends on the relative energies of the MOs of like symmetry. For homodiatomics ( homonuclear diatomic molecules), bonding σ orbitals have no nodal planes at which the wavefunction ...
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Lutetium
Lutetium is a chemical element with the symbol Lu and atomic number 71. It is a silvery white metal, which resists corrosion in dry air, but not in moist air. Lutetium is the last element in the lanthanide series, and it is traditionally counted among the rare earth elements. Lutetium is generally considered the first element of the 6th-period transition metals by those who study the matter, although there has been some dispute on this point. Lutetium was independently discovered in 1907 by French scientist Georges Urbain, Austrian mineralogist Baron Carl Auer von Welsbach, and American chemist Charles James. All of these researchers found lutetium as an impurity in the mineral ytterbia, which was previously thought to consist entirely of ytterbium. The dispute on the priority of the discovery occurred shortly after, with Urbain and Welsbach accusing each other of publishing results influenced by the published research of the other; the naming honor went to Urbain, as he had publ ...
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Rory Waterman (chemist)
Rory Waterman is an American chemist. He is a full professor and associate dean of inorganic, organometallic, and catalysis at the University of Vermont. Early life and education Waterman attended the University of Rochester for his Bachelor of Science and the University of Chicago for his Ph.D. After completing his doctoral degree in 2004, he accepted a two-year Miller Research Fellowship at the University of California, Berkeley. Career Waterman joined the University of Vermont's (UVM) College of Arts and Sciences as an assistant professor of chemistry in 2006. His research at UVM focuses on finding new ways to build chemical bonds, specifically in the chemical element Phosphorus. As a result of his research, he received the 2009 Alfred P. Sloan Award for outstanding early career scientists. Beyond this, Waterman also established research opportunities for Vermont high school and University of Vermont undergraduate students which resulted in him winning the 2009 Cottrell Scholar ...
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Cycloaddition
In organic chemistry, a cycloaddition is a chemical reaction in which "two or more unsaturated molecules (or parts of the same molecule) combine with the formation of a cyclic adduct in which there is a net reduction of the bond multiplicity". The resulting reaction is a cyclization reaction. Many but not all cycloadditions are concerted and thus pericyclic. Nonconcerted cycloadditions are not pericyclic. As a class of addition reaction, cycloadditions permit carbon–carbon bond formation without the use of a nucleophile or electrophile. Cycloadditions can be described using two systems of notation. An older but still common notation is based on the size of linear arrangements of atoms in the reactants. It uses parentheses: where the variables are the numbers of linear atoms in each reactant. The product is a cycle of size . In this system, the standard Diels-Alder reaction is a (4 + 2)-cycloaddition, the 1,3-dipolar cycloaddition is a (3 + 2)-cycloaddit ...
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Transition State
In chemistry, the transition state of a chemical reaction is a particular configuration along the reaction coordinate. It is defined as the state corresponding to the highest potential energy along this reaction coordinate. It is often marked with the double dagger ‡ symbol. As an example, the transition state shown below occurs during the SN2 reaction of bromoethane with a hydroxide anion: The activated complex of a reaction can refer to either the transition state or to other states along the reaction coordinate between reactants and products, especially those close to the transition state. Peter Atkins and Julio de Paula, ''Physical Chemistry'' (8th ed., W.H. Freeman 2006), p.809 According to the transition state theory, once the reactants have passed through the transition state configuration, they always continue to form products. History of concept The concept of a transition state has been important in many theories of the rates at which chemical reactio ...
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