Halides methane

Carbides may also be prepared, either by dhect carburizing, as in the case of steel, in which a surface carbide film dissolves into the subsuate steel, or by refractoty metal carbide formation as in die cases when one of the refractory metal halides is mixed with methane in the plasma gas. 

Abbreviations acac, acetylacetonate Aik, alkyl AN, acetonitrile bpy, 2,2 -bipyridine Bu, butyl cod, 1,5- or 1,4-cyclooctadiene coe, cyclooctene cot, cyclooctatetraene Cp, cyclopentadienyl Cp, pentamethylcyclopenladienyl Cy, cyclohexyl dme, 1,2-dimethoxyethane dpe, bis(diphenyl-phosphino)ethane dppen, cis-l,2-bis(di[Atenylphosphino)ethylene dppm, bis(diphenylphosphino) methane dppp, l,3-bis(diphenylphosphino)propane eda,ethylenediamine Et,ethyl Hal,halide Hpz, pyrazole HPz, variously substituted pyrazoles Hpz, 3,5-dimethylpyrazole Me, methyl Mes, mesityl nbd, notboma-2,5-diene OBor, (lS)-endo-(-)-bomoxy Ph, phenyl phen, LlO-phenanthroline Pr, f opyl py, pyridine pz, pyrazolate Pz, variously substituted pyrazolates pz, 3,5-dimethylpyrazolate solv, solvent tfb, tetrafluorobenzo(5,6]bicyclo(2.2.2]octa-2,5,7-triene (tetrafluorobenzobanelene) THE, tetrahydrofuran tht, tetrahydrothicphene Tol, tolyl. 

Although interesting from a mechanistic point of view, alkane halogenation is a poor synthetic method for preparing alkyl halides because mixtures of products invariably result. For example, chlorination of methane does not stop cleanly at the monochlorinated stage but continues to give a mixture of dichloro, trichloro, and even tetrachloro products. 

Carbon-carbon bond formation reactions and the CH activation of methane are another example where NHC complexes have been used successfully in catalytic applications. Palladium-catalysed reactions include Heck-type reactions, especially the Mizoroki-Heck reaction itself [171-175], and various cross-coupling reactions [176-182]. They have also been found useful for related reactions like the Sonogashira coupling [183-185] or the Buchwald-Hartwig amination [186-189]. The reactions are similar concerning the first step of the catalytic cycle, the oxidative addition of aryl halides to palladium(O) species. This is facilitated by electron-donating substituents and therefore the development of highly active catalysts has focussed on NHC complexes. 

Nonmetals form covalent molecular hydrides, which consist of discrete molecules. These compounds are volatile and many are Bronstcd acids. Some are gases— for example, ammonia, the hydrogen halides (HF, HC1, HBr, HI), and the lighter hydrocarbons such as methane, ethane, ethene, and ethyne. Liquid molecular hydrides include water and hydrocarbons such as octane and benzene. 

Because carbon bonds so readily with itself, there are many hydrocarbons (see Chapter 18). Silicon forms a much smaller number of compounds with hydrogen, called the silanes. The simplest silane is silane itself, SiH4, the analog of methane. Silane is formed by the action of lithium aluminum hydride on silicon halides in ether ... 

The deposition of carbides (carbidization) is usually obtained by reacting a halide with a hydrocarbon, such as methane, as follows ... 

Experiments have been carried out to mimic the reactions of model systems for coenzyme F430 that is involved in the terminal step in the biosynthesis of methane, and that is able to dechlorinate CCI4 successively to CHCI3 and CH2CI2 (Krone et al. 1989). Nickel(I) isobacteriochlorin anion was generated electrolytically and used to examine the reactions with alkyl halides in dimethylformamide (Helvenston and Castro 1992). The three classes of reaction were the same as those observed with Fe(II) deuteroporphyrin IX that have already been noted. 

Substituted thioureas have been extensively studied over the decades. Reaction of CoX2 (X = C1, Br) with substituted phenylthioureas yield a range of complexes involving halide and thiourea as ligands, characterized by spectroscopy and thermogravimetric analysis.503 Both [Co(Rtu)4(OH2)2]2+ (Rtu = thiourea, phenylthiourea, allylthiourea) and [Co(Rtu)2(OH2)4]2+ (Rtu = diphenylthiourea) have been prepared and characterized as low-spin octahedral species.504 The octahedral bis(phenylthiourea)bis(dithiolate)cobalt(II) complex, one of a number of complexes of phenylthiourea, chlorophenylthiourea and bis(diphenylphospinothioyl)methane prepared and characterized,505 proved the most biologically active of those tested. 

Cd (and Hg) complexes with bis- and tris(l-pyrazolyl)methanes and -ethanes, as well as with bis(l-triazolyl)methane, have been prepared and studied by conductance measurements (H20, dmso, and dimethylformamide (dmf) solutions), IR, far-IR, H, and 13C NMR spectrometries.203 The Cd halides form complexes of the type [CdLX2] complexes of the types [CdL2](C104)2 and [CdL3](BF4)2 are obtained from the respective Cd salts. 

The 1 1 complexes of alkynylgold compounds (L)AuC=CR with strong donors L can also be conveniently prepared from the corresponding gold halides (L)AuX (X = C1, Br, I), an alkyne HC=CR, and a base. For many representative examples, the reactions with an alkali alkanolate in an alcohol58 or with triethylamine in dichloro-methane are the methods of choice (Equation (13)).59... 

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