Formate ions reactions

We would like at this time to amplify the earlier brief comments on the catalytic decomposition of formate ion to H2 and C02 by the group 6b metal carbonyls. This process requires the presence of a vacant coordination site on the metal for formate binding, i.e., formation of m(C0)s02CH species. Consequently, the reaction of Cr(Co)0 with formate ion in 2-ethoxyetha-nol was found to take place under more rigorous conditions than those needed for the production of H2 in the Cr(C0)e/K0H system. That is, whereas Cr(C07e in aqueous K0H/2-ethoxyethanol commences to produce H2 at 50°C (where the rds appears to succeed the formation of Cr(C0)sH ), the analogous Cr(CO)e/formate ion reaction necessitates temperatures approaching 100°C. 

Generation of CO2 by VUV irradiation of aqueous solutions requires efficient scavenging by formic acid and formate ions [reactions (R2-R5)] of HO and H which are primarily formed by photolysis. Under the chosen experimental conditions, Caq are efficiently quenched by HsO". Other reactions of H, HO and e aq. such as recombination reactions leading to H2 and H2O2, respectively, and with the substituted benzenes should be negligible. 

The reaction has been applied to more complex enamines 13) and to dienamines 19). The reduction may be rationalized by initial protonation at the enamine carbon and subsequent decarboxylation of formate ion and addition of the hydride ion to the iminium cation. This mechanism has been given support by the reaction of the enamine (205) with deuterated formic acid 143) to give the corresponding amines. The formation of 206 on reaction with DCOOH clearly indicates that protonation at the enamine carbon is the initial step. 

The idea that dichlorocarbene is an intermediate in the basic hydrolysis of chloroform is now one hundred years old. It was first suggested by Geuther in 1862 to explain the formation of carbon monoxide, in addition to formate ions, in the reaction of chloroform (and similarly, bromoform) with alkali. At the end of the last century Nef interpreted several well-known reactions involving chloroform and a base in terms of the intermediate formation of dichlorocarbene. These reactions included the ring expansion of pyrroles to pyridines and of indoles to quinolines, as well as the Hofmann carbylamine test for primary amines and the Reimer-Tiemann formylation of phenols. 

Mechanism of bromohydrin formation by reaction of an alkene with Br2 in the presence of water. Water acts as a nucleophile to react with the intermediate bromonium ion. 

Mechanism of enamine formation by reaction of an aldehyde or ketone with a secondary amine, R2NH. The iminium ion intermediate has no hydrogen attached to N and so must lose H+ from the carbon two atoms away. 

Packer and Richardson (1975) and Packer et al. (1980) made use of the fact that electrons can be generated in water by y-radiation from a 60Co source (Scheme 8-29) to induce a free radical chain reaction between diazonium ions and alcohols, aldehydes, or formate ion. It has to be emphasized that the radiolytically formed solvated electron in Scheme 8-29 is only a part of the initiation steps (Scheme 8-30) by which an aryl radical is formed. The aryl radical initiates the propagation steps shown in Scheme 8-31. Here the alcohol, aldehyde, or formate ion (RH2) is the reducing agent (i.e., the electron donor) for the main reaction. The process is a hydro-de-diazoniation. 

Although the reverse of this reaction cannot be carried out directly, carbon monoxide does react with hydroxide ions in hot alkali to produce formate ions ... 

Acetylene Ion. No evidence for the contribution of ion-molecule reactions originating with acetylene ion to product formation has been obtained to date. By analogy with the two preceding sections, we may assume that the third-order complex should dissociate at pressures below about 50 torr. Unfortunately, the nature of the dissociation products would make this process almost unrecognizable. The additional formation of hydrogen and hydrogen atoms would be hidden in the sizable excess of the production of these species in other primary acts while the methyl radical formation would probably be minor compared with that resulting from ethylene ion reactions. The fate of the acetylene ion remains an unanswered question in ethylene radiolysis. 

Although carbonylation of the 2-norbomyl ion at or below room temperature leads to exclusive formation of the 2-ea o-norbomyloxo-carbonium ion, reactions at higher temperatures have shown that the 2-cwdo-norbornyloxocarbonium ion is just as stable as the exo-isomer (Hogeveen and Roobeek, 1969). This means that at low temperatures the carbonylation is kineticaUy controlled, and at high temperatures thermodynatnically controlled. The detailed free-enthalpy diagram in... 

The permanganate oxidation of formic acid has attracted much attention. The reaction is pH-independent above pH 5 and involves formate ion. At lower pH s the rate is much lower until permanganic acids begins to be formed at very low pH ... 

The ten-fold reduction in rate on deuteration without changing the stoichiometry provides strong evidence that both sets of products originate in a common step. The Arrhenius parameters for this reaction, E = 13.3 kcal.mole A5 = —17 eu) invite comparison with those for the oxidation of free formate ion E = 12.4 kcal.mole S AS = —15 eu). 

Oxidation of formic acid by mercuric chloride is the subject of several early kinetic studies. Dhar showed the reaction to be first-order in oxidant and substrate and to be subject to strong retardation by added chloride ions in agreement with earlier work. The reaction is also subject to retardation by added acid and presumably involves formate ion as the principal reactant. 

The mechanism of carbon dioxide reduction in aqueous and nonaqueous solutions was investigated by several authors. It is now generally accepted that the reduction of carbon dioxide to formate ions is a multistep reaction with the intermediate formation of free radicals CO2 and HCO2 either in the solution or adsorbed on the electrode ... 

Calorimetry investigations of zinc ions with functionalized pyridines have been carried out in both dimethylformamide and acetonitrile. The pyridines used were pyridine, 3-methylpyridine, and 4-methylpyridine. In DMF, for all three pyridines, four- and six-coordinate species formed and their formation constants, reaction enthalpies and entropies were determined. The stability increases linearly with increasing basicity of the pyridine derivative. The formation of the 3-methylpyridine complex is enthalpically less favorable and entropically more favorable than... 

Transfer hydrogenolysis of benzyl acetate was studied on Pd/C at room temperature using different formate salts.244 Hydrogen-donating abilities were found to depend on the counterion K+ > NH4 + > Na+ > Li+ > H+. Formate ion is the active species in this reaction. Adsorption of the formate ion on the Pd metal surface leads to dissociative chemisorption resulting in the formation of PdH- and C02. The kinetic isotope effect proves that the dissociative chemisorption of formate is the rate-limiting step. The adsorption and the surface reaction of benzyl acetate occurs very rapidly. 

Four years of study led to the discovery of glycine in the millimetre wavelength range in the hot molecular clouds of Sagittarius (around 81,500 light years away), Orion KL and W51. We can only conjecture as to the mechanism of its formation. Ion-molecule reactions in the gas phase, as well as UV photolytic processes in molecular ice, have been discussed. 

Fig. 5 Logarithmic plots of rate-equilibrium data for the formation and reaction of ring-substituted 1-phenylethyl carbocations X-[6+] in 50/50 (v/v) trifluoroethanol/water at 25°C (data from Table 2). Correlation of first-order rate constants hoh for the addition of water to X-[6+] (Y) and second-order rate constants ( h)so1v for the microscopic reverse specific-acid-catalyzed cleavage of X-[6]-OH to form X-[6+] ( ) with the equilibrium constants KR for nucleophilic addition of water to X-[6+]. Correlation of first-order rate constants kp for deprotonation of X-[6+] ( ) and second-order rate constants ( hW for the microscopic reverse protonation of X-[7] by hydronium ion ( ) with the equilibrium constants Xaik for deprotonation of X-[6+]. The points at which equal rate constants are observed for reaction in the forward and reverse directions (log ATeq = 0) are indicated by arrows.

There is experimental evidence that triplet states indeed play an important role in radical ion reactions. The formation of excimers has been suggested on the basis of chemiluminescence emission spectra, e.g. in the case of N-phenylcarbazole 15> and in some other experiments 18>. Other authors 19>20> have observed that the excimer fluorescence reported is probably produced by decomposition products of the radical ions or other impurities, as is very probably the so-called preannihilation chemiluminescence which occurs in electrogenerated chemiluminescence (see 21>). 

Figure 5 displays a typical time dependent trace of the hydrogen production during catalysis of the WGSR by Cr(CO)e. The decrease in activity of mature catalyst solutions is due to the consumption of KOH by C02, i.e., the formation of bicarbonate (C02 + 0H" HC03"). Reaction solutions prepared from Cr(CO)e with KHC03 as the added alkaline were much less active than their KOH counterparts. Experiments are planned at higher reaction temperatures in an effort to minimize this behavior. However, at 100° the Cr(C0) catalyst is quite active for the decomposition of formate ion to H2 plus C02 (vide infra). 

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