Carbon monoxide chemistry

1 Heterogeneous catalysis. In 1923, Fischer and Tropsch showed that carbon monoxide and hydrogen gave complex mixtures of hydrocarbons and 

Hydrocarbon formation is now believed to proceed via atomic carbon (carbide) to bridging methylene groups, and a chain polymerization process  

Developments in the 1930s led to zinc chromite for methanol synthesis, with pressures of about 300 atm-required for thermodynamic reasons at about 400°C. Reduction on a single metal centre seems a likely mechanism. The higher initial activity resulting from copper addition was known for many years, but the commercial success achieved by ICI and subsequent developers stems mainly from stabilization of the metal dispersion  

2 Hydroformylation. Experiments with supported cobalt catalysts led to the hydroformylation (or 0X0) process for the conversion of olefins and synthesis gas to aldehydes. Homogeneous catalysis followed, and is now used exclusively. The generally accepted mechanism involves the following reactions  

The order on carbon monoxide is negative, but a high partial pressure is required to maintain catalyst solubility and limit olefin hydrogenation. 

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J. W. Copenbaver and M. H. Bigelow, Mcetylene and Carbon Monoxide Chemistry, Reiobold Publishing Corp., New York, 1969, pp. 67—74. 

Copenhaver and Bigelow, Acetylene and Carbon Monoxide Chemistry, p. 124, Reinhold Publishing Corporation, New York 18, N. Y., 1949. 

Vinyl halides (example 17, Table VII) were first observed by Kroper to form acrylic esters by reaction with carbon monoxide under pressure and tetracarbonylnickel in methanol at 100°C. These reactions were later shown to occur under much milder conditions. Highly stereospecific reactions were observed c/s-vinyl halides gave cis-carbonylation products and trans-vinyl halides trans-carbonylation products (example 18, Table VII). Retention of configuration of alkyl substrates in carbonylation seems to be a general feature in carbon monoxide chemistry (193a). 

Although this classic picture evolved from "soft, mononuclear transition metal complexes suffices to explain a great deal of carbon monoxide chemistry, it is not clear that it is complete or accurate for understanding processes whereby CO is reduced, deoxygenated, and/or polymerized to form methane, long-chain hydrocarbons, alcohols, and other oxocarbons, especially in cases where heterogeneous catalysts or "hard" metals are involved (6, 7, ,9,J 0). This deficiency of information has led to the search for new modes of carbon monoxide reactivity and to attempts to understand carbon monoxide chemistry in nontraditional environments ... 

J.W. Copenhaver, MJL Bigelow, "Acetylene and Carbon Monoxide Chemistry", Reinhold Publ. Co., 1949. 

M.H.Bigelow,"Acetylene and Carbon Monoxide Chemistry," Reinhold,NY( 1949) 7)C. 

Carbon dioxide insertion reactions are potential intermediate steps in catalytic cycles leading to reduction of C02 or its incorporation into organic molecules. Analogies with carbon monoxide chemistry may be drawn, e.g., insertion reactions of carbon monoxide (20) play a key role in both the... 

These early successes with carbonyl complexes of rhenium encouraged me to undertake systematic research on the carbon monoxide chemistry of the heavy transition metals at our Munich Institute during the period 1939-45, oriented towards purely scientific objectives. The ideas of W. Manchot, whereby in general only dicarbonyl halides of divalent platinum metals should exist, were soon proved inadequate. In addition to the compounds [Ru(CO)2X2] (70), we were able to prepare, especially from osmium, numerous di- and monohalide complexes with two to four molecules of CO per metal atom (29). From rhodium and iridium (28) we obtained the very stable rhodium(I) complexes [Rh(CO)2X]2, as well as the series Ir(CO)2X2, Ir(CO)3X, [Ir(CO)3]j (see Section VII,A). With this work the characterization of carbonyl halides of most of the transition metals, including those of the copper group, was completed. 

Acetylene and Carbon Monoxide Chemistry, Reinhold, NY(1949) 14)J. W. Reppe... 

The study of stoichiometric CO insertions into transition metal complexes is of great importance because this reaction is the first step m the catalytic conversion of carbon dioxide. Hence, these investigations can lead to the possibility of introducing carbon dioxide into transition metal-catalyzed synthetic processes. Analogies with carbon monoxide chemistry may be drawn, for instance. from the CO insertion into metal alkyl bonds leading to such important industrial processes as hydroformylation and carbonylalion. 

The two philosophies are typically exemplified by hydroformylation (eq. (1)) [26] on the one hand and the Fischer-Tropsch reaction (eq. (2)) [7] on the other. They both represent catalytic carbon monoxide chemistry in the first case the molecular structure of the homogeneous catalyst (Structures 1 and 2) is precisely known to be trigonal-bipyramidal,... 

Carbon monoxide chemistry has been extensively studied, leading to a wide range of methods used in small scale organic syntheses up to industrial processes.8 Despite the versatility of carbonylation reactions, carbon monoxide suffers from major drawbacks that restricts its utilisation. From an industrial point of view, the cumbersome handling of this toxic gas necessitates very expensive facilities which prevent its use for the majority of fine chemical production processes. An alternative process equivalent to a carbonylation reaction which avoids carbon monoxide introduction into the reactor and that can be used in standard polyvalent type units would be of great interest. Of course, catalyst cost, stability and productivity should also fulfil economic requirements. 

The carbon monoxide chemistry observed here may be of relevance to mechanistic discussions of catalytic CO reduction, especially that involving actinide oxide or actinide oxide supported catalysts ... 

A. The publication of the classic reaction of carbon monoxide chemistry, the synthesis of methane in the presence of nickel and cobalt catalysts by P. Sabatier and J. B. Senderens in 1902. 

Zuo Y, Guerrero MA, and Jones RD (1998) Reassessment of the ocean to atmosphere flux of carbon monoxide. Chemistry and Ecology 14 241-257. 

The term carbonylation was first used by W.Reppe while working with syngas and carbon monoxide chemistry at BASF during the 1930s and 1940s. Carbonylations are catalytic reactions in which carbon monoxide, alone or with other compounds, is incorporated in an organic substrate. There are three general types of carbonylation reactions Reppe reactions, hydroformylations, and Koch carbonylations. 

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