Fluxional moleculeIn chemistry and molecular physics, fluxional (or non-rigid) molecules are molecules that undergo dynamics such that some or all of their atoms interchange between symmetry-equivalent positions. Because virtually all molecules are fluxional in some respects, e.g. bond rotations in most organic compounds, the term fluxional depends on the context and the method used to assess the dynamics. Often, a molecule is considered fluxional if its spectroscopic signature exhibits line-broadening (beyond that dictated by the Heisenberg uncertainty principle) due to chemical exchange.
Molecular vibrationA molecular vibration is a periodic motion of the atoms of a molecule relative to each other, such that the center of mass of the molecule remains unchanged. The typical vibrational frequencies range from less than 1013 Hz to approximately 1014 Hz, corresponding to wavenumbers of approximately 300 to 3000 cm−1 and wavelengths of approximately 30 to 3 μm. For a diatomic molecule A−B, the vibrational frequency in s−1 is given by , where k is the force constant in dyne/cm or erg/cm2 and μ is the reduced mass given by .
Mond processThe Mond process, sometimes known as the carbonyl process, is a technique created by Ludwig Mond in 1890, to extract and purify nickel. The process was used commercially before the end of the 19th century, and particularly by the International Nickel Company in the Sudbury Basin. This process converts nickel oxides into nickel metal with very high purity being attainable in just a single step. This process involves the fact that carbon monoxide combines with nickel readily and reversibly to give nickel carbonyl.
Carbonyl ironCarbonyl iron is a highly pure (97.5% for grade S, 99.5+% for grade R) iron, prepared by chemical decomposition of purified iron pentacarbonyl. It usually has the appearance of grey powder, composed of spherical microparticles. Most of the impurities are carbon, oxygen, and nitrogen. BASF invented carbonyl iron powder in 1925 and claims to be the world's leading producer. In 1934, BASF was also involved in the development of the very first magnetic tapes used by the AEG Magnetophon tape recorder.
Dissociative substitutionIn chemistry, dissociative substitution describes a reaction pathway by which compounds interchange ligands. The term is typically applied to coordination and organometallic complexes, but resembles the SN1 mechanism in organic chemistry. This pathway can be well described by the cis effect, or the labilization of CO ligands in the cis position. The opposite pathway is associative substitution, being analogous to SN2 pathway. Pathways that are intermediate between the pure dissociative and pure associative pathways are called interchange mechanisms.
Metal-phosphine complexA metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0). Many metal phosphine complexes are prepared by reactions of metal halides with preformed phosphines.
Organoruthenium chemistryOrganoruthenium chemistry is the chemistry of organometallic compounds containing a carbon to ruthenium chemical bond. Several organoruthenium catalysts are of commercial interest and organoruthenium compounds have been considered for cancer therapy. The chemistry has some stoichiometric similarities with organoiron chemistry, as iron is directly above ruthenium in group 8 of the periodic table. The most important reagents for the introduction of ruthenium are ruthenium(III) chloride and triruthenium dodecacarbonyl.
Cativa processThe Cativa process is a method for the production of acetic acid by the carbonylation of methanol. The technology, which is similar to the Monsanto process, was developed by BP Chemicals and is under license by BP Plc. The process is based on an iridium-containing catalyst, such as the complex [Ir(CO)2I2]− (1). The Cativa and Monsanto processes are sufficiently similar that they can use the same chemical plant. Initial studies by Monsanto had shown iridium to be less active than rhodium for the carbonylation of methanol.
Organoiron chemistryOrganoiron 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. While iron adopts oxidation states from Fe(−II) through to Fe(VII), Fe(IV) is the highest established oxidation state for organoiron species. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals.
