Reactions Involving Carbon Monoxide

A -Heterocyclic Carbene Complexes in Reactions Involving Carbon Monoxide... 

High pressure infrared (HP IR) spectroscopy has now been used for over 30 years for the study of homogeneous transition metal catalysed processes. The technique is particularly useful for reactions involving carbon monoxide, for which transition metal carbonyl complexes are key intermediates in the catalytic mechanisms. Such complexes have one or more strong r(CO) absorptions, the frequencies and relative intensities of which provide information about the geometry and electronic character of the metal center. As well as probing the metal species, HP IR spectroscopy can also be used to monitor the depletion and formation of organic reactants and products if they have appropriate IR absorptions. 

Other additions, such as addition of alkyl halides and carbonyl compounds, are discussed in Chapter 5, whereas Chapter 7 covers addition reactions involving carbon monoxide (hydroformylation, carboxylations). Hydrogen addition is discussed in Chapter 11. The nucleophilic addition of organometallics to multiple bonds is of great significance in the anionic polymerization of alkenes and dienes and is treated in Chapter 13. 

The group transfer ability of organoselenium compounds [17] has been applied to a three-component coupling reaction involving carbon monoxide (Scheme 6.10)... 

One-electron oxidation systems can also generate radical species in non-chain processes. The manganese(III)-induced oxidation of C-H bonds of enolizable carbonyl compounds [74], which leads to the generation of electrophilic radicals, has found some applications in multicomponent reactions involving carbon monoxide. In the first transformation given in Scheme 6.49, a one-electron oxidation of ethyl acetoacetate by manganese triacetate, yields a radical, which then consecutively adds to 1-decene and CO to form an acyl radical [75]. The subsequent one-electron oxidation of an acyl radical to an acyl cation leads to a carboxylic acid. The formation of a y-lactone is due to the further oxidation of a carboxylic acid having an active C-H bond. As shown in the second equation, alkynes can also be used as substrates for similar three-component reactions, in which further oxidation is not observed [76]. 

After having discussed catalytic reactions involving carbon monoxide, hydrogen, carbon monoxide and hydrogen, as well as carbon monoxide and water, this section is dedicated mainly to isomerization and rearrangement reactions and to carbon-carbon and carbon-nitrogen coupling reactions. 

We include in this section formylation reactions involving carbon monoxide, hydrogen cyanide, formyl fluoride and dichloromethyl alkyl ethers." The Vilsmeier and Reimer-Tiemann formylation reactions are the subjects of other chapters (Volume 2, Chapters 3.4 and 3.5). 

Side Reactions Involving Carbon Monoxide, Ethylene, and Water Catalyst Niokel-kieselguhr (30 70). Reaction temperature 180°. Final pressure 3000-3S(K) p.s.i.g. 

From a study of the various side reactions involving carbon monoxide, ethylene, and water under the synthesis conditions of temperature, pressure, and catalyst (Table II), it appears that the important reactions taking place in the system are ... 

Further results on the reduction of copper(ii) to copper(i) by carbon monoxide indicate parallel reactions involving carbon monoxide insertion into a copper-hydroxide bond, as described for cobalt(n) reduction above, and formation of the stable Cu(CO)+ cation. ... 

Values for the partition coefficient of other nonmammalian heme proteins, most of which have been determined spectroscopically, show wide variations. Representative values taken from Keilin are shown in Table XI. This table also contains values of the span, that is, the shift in wave length of the a band of the absorption spectrum of the protein, wherever known. It used to be thought that this shift was proportional to log a, which is itself proportional to the free energy of the exchange reaction involving carbon monoxide and oxygen but, as... 

The scope of the book is largely confined to the most recent developments in carbonylation chemistry. Since this book of special focus is not intended to go into the fine details of homogeneous catalysis as well as its historical background, only the most recent achievements of carbonylation chemistry are discussed. I believe there is no need to elaborate further on the earlier findings in view of the excellent textbooks already available. During the last decade, several novel synthetic reactions involving carbon monoxide have been discovered, as well as new methods such as biphasic carbonylation or application of ionic liquids have been developed. It is our purpose to provide a perspective of this formative period through the contributions of the experts on special topics of carbon monoxide activation by transition metals. 

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