Water-assisted reaction mechanisms

The bulk solvent effect on the reaction energy, described by the lower portion of Scheme 2.3, significantly modifies the relative importance of the uncatalyzed and water-assisted alkylation mechanism by o-QM in comparison to the gas phase. 

The combination of NOx trapping materials with NH3-SCR catalysts for the NOx treatment from mobile lean-burn engines has been reported. Particular attention has been paid in the mechanism of ammonia emission and reactivity toward NOx abatement in NSR process. For the first point, two reaction paths are proposed in the literature. In the presence of hydrogen during the rich pulses of the LNT regeneration, ammonia can be formed by direct reaction with the previously stored NOx. When CO is use as the reductant agent, water-assisted reaction, by hydrolysis of intermediate isocyanate species, is suggested. In the presence of water and carbon dioxide in the gas mixture, both reaction pathways co-exist due to direct and reverse water gas shift reaction. Ammonia is thereafter involved in the NOx reduction mechanism, by a sequential route in which NH3 reacts faster with NOx to yield N2 compared with its own formation rate. It is found that both the nature and the content of the basic element as well as the redox properties of the support interfere in NH3 yield. 

These profiles clearly show that in the gas phase the alkylations of both ammonia and water by o-QM are assisted by an additional water molecule H-bonded to o-QM (water-catalyzed mechanism), since S4 and S5 TSs are favored over their uncatalyzed counterparts (SI and S2) by 5.6 and4.0 kcal/mol [at the B3LYP/6-311 + G(d,p) level], respectively. In contrast, the reaction with hydrogen sulfide in the gas phase shows a slight preference for a direct alkylation without water assistance (by 0.8 kcal/mol). 

Possible Xanthine Oxidase Mechanism. The proposed reaction mechanism, (Figure 27), which must still be regarded as a working hypothesis, entails metal binding of substrate, metal-assisted activation of water, CEPT, and stabilization of the hydrosulfido ligand. 

The photochemical alkylation of olefins by nitriles and ketones is not straightforward, due mainly to the inefficient abstraction of hydrogen from an electron-withdrawing-substituted carbon by an electrophile such as the photocatalyst excited state. Nevertheless, various methyl ketones have been synthesized by the irradiation of a ketone/oleftn mixture dissolved in aqueous acetone. The mechanism of the reaction remains to be clarified, but a water-assisted C—C coupling between an acetonyl radical and the olefin has been postulated (Scheme 3.12). The reaction has several advantages, as it is cheap (an acetone/water mixture is used as the solvent) and occurs under mild metal-free conditions with no need for a photocatalyst [28],... 

Terpene synthases, also known as terpene cyclases because most of their products are cyclic, utilize a carbocationic reaction mechanism very similar to that employed by the prenyltransferases. Numerous experiments with inhibitors, substrate analogues and chemical model systems (Croteau, 1987 Cane, 1990, 1998) have revealed that the reaction usually begins with the divalent metal ion-assisted cleavage of the diphosphate moiety (Fig. 5.6). The resulting allylic carbocation may then cyclize by addition of the resonance-stabilized cationic centre to one of the other carbon-carbon double bonds in the substrate. The cyclization is followed by a series of rearrangements that may include hydride shifts, alkyl shifts, deprotonation, reprotonation and additional cyclizations, all mediated through enzyme-bound carbocationic intermed iates. The reaction cascade terminates by deprotonation of the cation to an olefin or capture by a nucleophile, such as water. Since the native substrates of terpene synthases are all configured with trans (E) double bonds, they are unable to cyclize directly to many of the carbon skeletons found in nature. In such cases, the cyclization process is preceded by isomerization of the initial carbocation to an intermediate capable of cyclization. 

Mechanisms (C) and (D) have been proposed to rationalize the oxygen-assisted reaction at 440 K, shown in equation 24. It is impossible to distinguish the routes (C) and (D) since the hydroxyl disproportionation and the reaction of H(a) and 0(a) to form water are fast at the reaction temperature. The role of oxygen in the C—H bond-breaking process has not been exposed precisely by Brainard and Madix31. 

This picture resembles Yamamoto s Lewis acid assisted Brpnsted acidity [43] furthermore, the strategy of increasing the nucleophihcity of alcohols and water by precoordination to Lewis acids is generally found in enzymatic reaction mechanisms... 

In this chapter we have discussed the carbonylative transformations of C-X bonds using amines, alcohols and water as nucleophiles. From a reaction mechanism point of view, they all go through a nucleophilic attack on the acylmetal species by nucleophiles. No reductive elimination step was involved, and the active catalyst was regenerated under the assistant of base. 

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