|
Tolman's Rule
Tolman's rule states that, in a certain chemical reaction, the steps involve exclusively intermediates of 18- and 16 electron configuration. The rule is an extension of the 18-electron rule. This rule was proposed by American chemist Chadwick A. Tolman. As stated above, Tolman's rule, even for reactions that proceed via 2e− steps, is incorrect because many reactions involve configurations of fewer than 16 e−. Many examples of homogeneous catalysis involving organometallic complexes involve shuttling of complexes between 16 and 18 electron configurations. 16-electron complexes often form adducts with Lewis bases and, if low-valent, undergo oxidative addition. : Conversely, complexes of 18 electron configuration tend to dissociate ligands or undergo reductive elimination: : See also * Electron counting Electron counting is a formalism used for classifying compounds and for explaining or predicting electronic structure and bonding. Many rules in chemistry rely on electr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chadwick A
Chadwick may refer to: People * Chadwick (surname) * Chadwick (given name) Places * Chadwick, Illinois, United States, a village * Chadwick, Michigan, United States, a former community * Chadwick, Missouri, United States, an unincorporated community * Chadwick Bay, New York, United States * Chadwick Lake, New York, United States * Chadwick, Western Australia, a suburb of the town of Esperance * Chadwick (crater), a lunar crater Other uses * James Chadwick Medal and Prize, a biennial award presented by Institute of Physics for particle physics research * Chadwick Arboretum, Columbus, Ohio * The Chadwick, an apartment building in Indianapolis, Indiana, formerly on the National Register of Historic Places * Chadwick School Chadwick School is a nonsectarian independent K-12 day school located in an unincorporated area on the Palos Verdes Peninsula in Los Angeles County, California, United States. Specifically it is located at the top of the neighborhood referred to ... ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lewis Base
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any species that has a filled orbital containing an electron pair which is not involved in bonding but may form a dative bond with a Lewis acid to form a Lewis adduct. For example, NH3 is a Lewis base, because it can donate its lone pair of electrons. Trimethylborane (Me3B) is a Lewis acid as it is capable of accepting a lone pair. In a Lewis adduct, the Lewis acid and base share an electron pair furnished by the Lewis base, forming a dative bond. In the context of a specific chemical reaction between NH3 and Me3B, a lone pair from NH3 will form a dative bond with the empty orbital of Me3B to form an adduct NH3•BMe3. The terminology refers to the contributions of Gilbert N. Lewis. From p. 142: "We are inclined to think of substances as p ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Oxidative Addition
Oxidative addition and reductive elimination are two important and related classes of reactions in organometallic chemistry. Oxidative addition is a process that increases both the oxidation state and coordination number of a metal centre. Oxidative addition is often a step in catalytic cycles, in conjunction with its reverse reaction, reductive elimination. Role in transition metal chemistry For transition metals, oxidative reaction results in the decrease in the d''n'' to a configuration with fewer electrons, often 2e fewer. Oxidative addition is favored for metals that are (i) basic and/or (ii) easily oxidized. Metals with a relatively low oxidation state often satisfy one of these requirements, but even high oxidation state metals undergo oxidative addition, as illustrated by the oxidation of Pt(II) with chlorine: : tCl4sup>2− + Cl2 → tCl6sup>2− In classical organometallic chemistry, the formal oxidation state of the metal and the electron count of the complex bot ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Reductive Elimination
Reductive elimination is an elementary step in organometallic chemistry in which the oxidation state of the metal center decreases while forming a new covalent bond between two ligands. It is the microscopic reverse of oxidative addition, and is often the product-forming step in many catalytic processes. Since oxidative addition and reductive elimination are reverse reactions, the same mechanisms apply for both processes, and the product equilibrium depends on the thermodynamics of both directions. General information Reductive elimination is often seen in higher oxidation states, and can involve a two-electron change at a single metal center (mononuclear) or a one-electron change at each of two metal centers (binuclear, dinuclear, or bimetallic). For mononuclear reductive elimination, the oxidation state of the metal decreases by two, while the d-electron count of the metal increases by two. This pathway is common for d8 metals Ni(II), Pd(II), and Au(III) and d6 metals P ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electron Counting
Electron counting is a formalism used for classifying compounds and for explaining or predicting electronic structure and bonding. Many rules in chemistry rely on electron-counting: *Octet rule is used with Lewis structures for main group elements, especially the lighter ones such as carbon, nitrogen, and oxygen, * 18-electron rule in inorganic chemistry and organometallic chemistry of transition metals, *Hückel's rule for the π-electrons of aromatic compounds, *Polyhedral skeletal electron pair theory for polyhedral cluster compounds, including transition metals and main group elements and mixtures thereof, such as boranes. Atoms are called "electron-deficient" when they have too few electrons as compared to their respective rules, or " hypervalent" when they have too many electrons. Since these compounds tend to be more reactive than compounds that obey their rule, electron counting is an important tool for identifying the reactivity of molecules. Counting rules Two me ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ar ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemical Bonding
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Empirical Laws
Scientific laws or laws of science are statements, based on repeated experiments or observations, that describe or predict a range of natural phenomena. The term ''law'' has diverse usage in many cases (approximate, accurate, broad, or narrow) across all fields of natural science ( physics, chemistry, astronomy, geoscience, biology). Laws are developed from data and can be further developed through mathematics; in all cases they are directly or indirectly based on empirical evidence. It is generally understood that they implicitly reflect, though they do not explicitly assert, causal relationships fundamental to reality, and are discovered rather than invented. Scientific laws summarize the results of experiments or observations, usually within a certain range of application. In general, the accuracy of a law does not change when a new theory of the relevant phenomenon is worked out, but rather the scope of the law's application, since the mathematics or statement represent ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
