Carbon monoxide with protons

In both homogeneous and heterogeneous catalysis, carbon monoxide activation involves first the coordinaiive interaction of carbon monoxide with a metal acceptor center. Carbon monoxide, being a weak donor base, does not react with a proton and produces only a vety weak interaction with a hard acid center such as BH3, With less hard Lewis centers, such as CuX, AgX, AuXj etc. (X - halogen), more or less stable carbon monoxide adducts can be isolated. A variety of modes of CO coordination in well characterized organometallic complexes is known. Scheme 1 contains some selected examples. 

Despite the presence of a formally divalent carbon atom, CO is not in fact a particularly reactive molecule and much of its chemistry depends on the use of either extreme conditions, energetic reagents or some form of catalysis. Perhaps the simplest examples of such catalysis are found in the reactions of carbon monoxide with protic reagents such as alcohols or secondary amines, affording esters or amides of formic acid. These reactions are catalyzed by alkoxide or amide anions, respectively, and, as shown in Scheme 1, the key step is nucleophilic attack on CO by the catalyst to give a strongly basic alkoxyacyl or aminoacyl anion which is immediately trapped by proton transfer from the alcohol or amine, so generating the catalytic species. 

Formylation of aromatic rings with carbon monoxide requires the use of superacidics to activate carbon monoxide by protonation and to protonate the formed aldehyde which is the thermodynamic driving force of the reaction. 

A chloro-bridged cyclopalladated pyridine compound is also carbonylated by the reaction of carbon monoxide with bubbling through a reaction mixture at room temperature in the presence of NEts as a proton scavenger. Metalhc palladium is separated out, while ethyl ester 7.62 is recovered in a 73 % yield, as shown in Eq. (7.41) [94]. 

Abstract To date, microcalorimetry of CO adsorption onto supported metal catalysts was mainly used to study the effects induced by the nature and the particle size of supported metallic clusters, the conditions of pretreatment and the support materials on the surface properties of the supported metallic particles. The present chapter focuses on the employ of adsorption microcalorimetry for studying the interaction of carbon monoxide with platinum-based catalyst aimed to be used in proton exchange membrane fuel cells (PEMFCs) applications. 

Acyclic (ri -diene)iron complexes will give substituted cyclopentanones or y,5-unsaturated aldehydes upon treatment with nucleophiles under carbon monoxide atmosphere (Scheme 4-119). A proposed mechanism involves the addition of the nucleophile at an inner carbon atom of the t) -diene ligand followed by insertion of carbon monoxide. Subsequent protonation provides the unsaturated aldehyde. Alternatively, the acyliron intermediate can undergo carboferration to give an acyliron intermediate. Isomerization via (3-hydride elimination and readdition provides an iron-enolate anion that upon treatment with acid provides the cyclopentanone. ... 

Protonation of formic acid similarly leads, after the formation at low temperature of the parent carboxonium ion, to the formyl cation. The persistent formyl cation was observed by high-pressure NMR only recently (Horvath and Gladysz). An equilibrium with diprotonated carbon monoxide causing rapid exchange can be involved, which also explains the observed high reactivity of carbon monoxide in supera-cidic media. Not only aromatic but also saturated hydrocarbons (such as isoalkanes and adamantanes) can be readily formylated. 

Intermediate formation of formyl chloride is not necessary since the actual alkylating agent, HCO", can be produced by protonation of carbon monoxide or its complexes. However, it is difficult to obtain an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide. Suitable laboratory preparations involve the reaction of chlorosulfonic acid with formic acid or the reaction of ben2oyl chloride with formic acid ... 

The Lewis definition of a base is broader than the Bronsted definition. That is, although every Bronsted base is a Lewis base, not every Lewis base is a Bronsted base. For instance, carbon monoxide is an important Lewis base in its reactions with metals, but it is not a Bronsted base because it does not accept protons. 

Chloroform is more rapidly hydrolyzed with base than dichloromethane or carbon tetrachloride and gives not only formic acid but also carbon monoxide Hine has shown that the mechanism of chloroform hydrolysis is quite different from that of dichloromethane or carbon tetrachloride, though superficially the three reactions appear similar. The first step is the loss of a proton to give CCla , which then loses Cl to give dichlorocarbene CCI2, which is hydrolyzed to formic acid or carbon monoxide. 

When acid catalysts are employed, in the absence of nickel carbonyl, the mechanism involves initial attack by a proton, followed by attack of the resulting carbocation on carbon monoxide to give an acyl cation, which, with water, gives the product ... 

The pH dependence of nitrogenase activity has been interpreted in terms of a group with a pi a = 6.3 that must he deprotonated for activity and another group with a pi a = 9 that must be protonated for activity 128). The pi a of the latter group was moved about 0.5 pH units more acid in the presence of acetylene and carbon monoxide and the group with the pi of 6.3 was moved about 0.4 pH units more acid by acetylene. The behavior of the group with the pZa of 9 is fully consistent with earlier observations (50) on the effect of acetylene on... 

The authors developed a multi-layered microreactor system with a methanol reforma- to supply hydrogen for a small proton exchange membrane fiiel cell (PEMFC) to be used as a power source for portable electronic devices [6]. The microreactor consists of four units (a methanol reformer with catalytic combustor, a carbon monoxide remover, and two vaporizers), and was designed using thermal simulations to establish the rppropriate temperature distribution for each reaction, as shown in Fig. 3. 

The intramolecular cyclization of l,2-dien-7-ynes and l,2-dien-6-ynes regiospecifically affords the corresponding titanacycles, which react with protons, carbon monoxide, aldehydes, or imines to give single products, as shown in Eqs. 9.56 and 9.57 [102], As the formation of titanacycles and their subsequent reaction with externally added reagents such as carbon monoxide (Eq. 9.56) or an aldehyde (or imine) (Eq. 9.57) proceeds with excellent chirality transfer, this represents a new method for synthesizing optically active cyclopentane derivatives from optically active allenes [102]. 

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