Carbon monoxide, reaction with organic

Titanium carbide may also be made by the reaction at high temperature of titanium with carbon titanium tetrachloride with organic compounds such as methane, chloroform, or poly(vinyl chloride) titanium disulfide [12039-13-3] with carbon organotitanates with carbon precursor polymers (31) and titanium tetrachloride with hydrogen and carbon monoxide. Much of this work is directed toward the production of ultrafine (<1 jim) powders. The reaction of titanium tetrachloride with a hydrocarbon-hydrogen mixture at ca 1000°C is used for the chemical vapor deposition (CVD) of thin carbide films used in wear-resistant coatings. 

The bonding between carbon monoxide and transition-metal atoms is particularly important because transition metals, whether deposited on soHd supports or present as discrete complexes, are required as catalysts for the reaction between carbon monoxide and most organic molecules. A metal—carbon ( -bond forms by overlapping of metal orbitals with orbitals on carbon. Multiple-bond character between the metal and carbon occurs through formation of a metal-to-CO TT-bond by overlap of metal-i -TT orbitals with empty antibonding orbitals of carbon monoxide (Fig. 1). 

Organopalladium intermediates are also involved in the synthesis of ketones and other carbonyl compounds. These reactions involve acylpalladium intermediates, which can be made from acyl halides or by reaction of an organopalladium species with carbon monoxide. A second organic group, usually arising from any organometallic reagent, can then form a ketone. Alternatively, the acylpalladium intermediate may react with nucleophilic solvents such as alcohols to form esters. 

Isomeric (s-cis- and (i-fra/w-V-conjugated diene)zirconocene and -haf-nocene complexes exhibit pronounced differences in their characteristic structural data as well as their spectroscopic features. These differences exceed by far the consequences expected to arise simply from the presence of conformational isomers of the 1,3-diene unit. While (f-rra/u-butadiene)-zirconocene (3a) shows a behavior similar to a transition metal olefin TT-complex, the (.r-cu-diene)ZrCp2 isomer 5a exhibits a pronounced alkylmetal character (23, 45). Typical features are best represented by a tr, 7T-type structure for 5 (55). However, the distinctly different bonding situation of the butadiene Tr-system/bent-metallocene linkage is not only reflected in differences in physical data between the dienemetallocene isomers 3 and 5, but also gives rise to markedly different chemical behavior. Three examples of this are discussed in this section the reactions of the 3/5 isomeric mbcture with carbon monoxide, ethylene, and organic carbonyl compounds. 

Oxidizer, Poison, Corrosive SAFETY PROFILE Poisonous and corrosive. Very reactive, a powerful oxidizer. Explosive or violent reaction with organic materials, water, acetone, ammonium halides, antimony, antimony trichloride oxide, arsenic, benzene, boron, bromine, carbon, carbon monoxide, carbon tetrachloride, carbon tetraiodide, chloromethane, cobalt, ether, halogens, iodine, powdered molybdenum, niobium, 2-pentanone, phosphoms, potassium hexachloroplatinate, pyridine, silicon, silicone grease, sulfur, tantalum, tin dichloride, titanium, toluene, vanadium, uranium, uranium hexafluoride. 

The preparation, properties, and reactions, especially polymerization, of products from the acetylene-carbon monoxide reaction, such as acrylic acid and its esters, are given by Blout and Mark (8) and by Schildknecht (98). Similarly treated therein are the vinyl esters from acetylene and carboxylic acids, and other vinylation products such as vinyl ethers. The esterification of organic acids with olefins is reviewed by Morin and Bearse (76). 

The anions generated from tetracarbonyl(phosphine) carbene complexes are more reactive in their reactions with organic electrophiles. This is consistent with the observation that the pATa of the methyl pentacarbonyl complex (88a) is increased by six orders of magnitude when one of the carbon monoxide ligands is replaced with tributylphosphine. The anion generated from (106) will give good yields of alkylated products with simple alkyl halides such as ethyl bromide however, dialkylation is still a serious side reaction. It has been reported that both pentacarbonyl and tetracarbonyl(phosphine) complexes can be efficiently monoalkylated with alkyl triflates (primary and secondary). The anion (89) for example, can be monoalkyated with the 3-butenyl triflate in 80% yield. ... 

Carbon atoms, energetic, reactions with organic compounds, 3, 201 Carbon monoxide, reactivity of carbonium ions towards, 10, 29... 

Cobalt has an odd number of electrons, and does not form a simple carbonyl in oxidation state 0. However, carbonyls of formulae Co2(CO)g, Co4(CO)i2 and CoJCO),6 are known reduction of these by an alkali metal dissolved in liquid ammonia (p. 126) gives the ion [Co(CO)4] ". Both Co2(CO)g and [Co(CO)4]" are important as catalysts for organic syntheses. In the so-called oxo reaction, where an alkene reacts with carbon monoxide and hydrogen, under pressure, to give an aldehyde, dicobalt octacarbonyl is used as catalyst ... 

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