Chemical 1,1-proton transfer

A second advantage of water is that in addition to being able to dissolve electrolytes by the physical forces involved in solvation, it is also able to undergo chemical proton-transfer reactions with potential electrolytes and produce ionic solutions. Water is able to donate protons to, and to receive protons from, molecules of potential electrolytes. Thus, water can function as both a source and a sink for protons and consequently can enter into ion-forming reactions with a particularly large range of substances. This is why potential electrolytes often react best with water as a partner in the proton-transfer reactions. Finally, water is stable both chemically and physically at ambient temperature, unlike many organic solvents which tend to evaporate (Table 4.24) or decompose slowly with time. 

The basic character of benzidine affords an alternate mechanism to influence the average position of the bead. Protonation of the amine functional groups by simple addition of trifluoroacetic acid (TFA) to the solution also generates positive charges on the benzidine unit and forces the bead to encircle the biphenol station. Neutralization with base (pyridine) returns the system to its initial state by removing the positive charges on the benzidine station (Scheme 6). These phenomena were verified in careful JH-NMR spectroscopic experiments [7], Thus, chemical (proton transfer) reactions are also useful to control the sliding motion of the macrocyclic bead in this rotaxane. 

Several processes are unique to ions. A common reaction type in which no chemical rearrangement occurs but rather an electron is transferred to a positive ion or from a negative ion is tenued charge transfer or electron transfer. Proton transfer is also conunon in both positive and negative ion reactions. Many proton- and electron-transfer reactions occur at or near the collision rate [72]. A reaction pertaining only to negative ions is associative detaclunent [73, 74],... 

Proton transfers from strong acids to water and alcohols rank among the most rapid chemical processes and occur almost as fast as the molecules collide with one another Thus the height of the energy barrier the activation energy for proton transfer must be quite low... 

The chain polymerization of formaldehyde CH2O was the first example of a chemical conversion for which the low-temperature limit of the rate constant was discovered (see reviews by Goldanskii [1976, 1979]). As found by Mansueto et al. [1989] and Mansueto and Wight [1989], the chain growth is driven by proton transfer at each step of adding a new link... 

A catalyst is defined as a substance that influences the rate or the direction of a chemical reaction without being consumed. Homogeneous catalytic processes are where the catalyst is dissolved in a liquid reaction medium. The varieties of chemical species that may act as homogeneous catalysts include anions, cations, neutral species, enzymes, and association complexes. In acid-base catalysis, one step in the reaction mechanism consists of a proton transfer between the catalyst and the substrate. The protonated reactant species or intermediate further reacts with either another species in the solution or by a decomposition process. Table 1-1 shows typical reactions of an acid-base catalysis. An example of an acid-base catalysis in solution is hydrolysis of esters by acids. 

Whenever possible, the chemical reactions involved in the fonnation of diastereomers and their- conversion to separate enantiomers are simple acid-base reactions. For example, naturally occurring (5)-(—)-malic acid is often used to resolve fflnines. One such amine that has been resolved in this way is 1-phenylethylarnine. Amines are bases, and malic acid is an acid. Proton transfer from (5)-(—)-malic acid to a racemic mixture of (/ )- and (5)-1-phenylethylarnine gives a mixture of diastereorneric salts. 

Much information on proton transfers has been obtained by NMR chemical exchange studies. An example is the proton exchange between neopentyl alcohol and acetic acid in acetic acid as the solvent. The reaction is... 

Since the domain explored will always be a very small part of the possible cases of tautomerism, it is essential to have general rules for families of compounds, substituents, and solvents. This chemical approach is maintained in this chapter, although the importance of the calculations is recognized. The following discussion begins with calculation of tautomeric equilibrium constants, followed by the combined use of theoretical calculations and experimental results (an increasingly expanding field) and ends with the calculations of the mechanisms of proton transfer between tautomers. 

Many computational studies in heterocyclic chemistry deal with proton transfer reactions between different tautomeric structures. Activation energies of these reactions obtained from quantum chemical calculations need further corrections, since tunneling effects may lower the effective barriers considerably. These effects can either be estimated by simple models or computed more precisely via the determination of the transmission coefficients within the framework of variational transition state calculations [92CPC235, 93JA2408]. 

We can use this more general view to discuss the strengths of acids. In our generalized acid-base reaction (52), the proton transfer implies the chemical bond in HB, must be broken and the chemical bond in HB2 must be formed. If the HB, bond is easily broken, then HB, will be a strong acid. Then equilibrium will tend to favor a proton transfer from HB, to some other base, B2. If, on the other hand, the HB, bond is extremely stable, then this substance will be a weak acid. Equilibrium will tend to favor a proton transfer from some other acid, HB2, to base B, forming the stable HB, bond. 

J.ll In each of the following salts, either the cation or the anion is a weak acid or a weak base. Write the chemical equation for the proton transfer reaction of this cation or anion with water (a) NaC6H50 (b) KCIO (c) C,HSNHCI ... 

J.12 C6HsNH3C1 is a chloride salt with an acidic cation, (a) If 50.0 g of C6H5NH3C1 is dissolved in water to make 150.0 mL of solution, what is the initial molarity of the cation (b) Write the chemical equation for the proton transfer reaction of the cation with water. Identify the acid and the base in this reaction. 

J.I3 Na As04 is a salt of a weak base that can accept more than one proton, (a) Write the chemical equations for the sequential proton transfer reactions of the anion with water. Identify the acid and the base in each reaction, (b) If 35.0 g of Na3As04 is dissolved in water to make 250.0 ml. of solution, how many moles of sodium cations are in the solution ... 

Like all chemical equilibria, this equilibrium is dynamic and we should think of protons as ceaselessly exchanging between HCN and H20 molecules, with a constant but low concentration of CN and H30+ ions. The proton transfer reaction of a strong acid, such as HCl, in water is also dynamic, but the equilibrium lies so strongly in favor of products that we represent it just by its forward reaction with a single arrow. 

The label am " indicates a species dissolved in liquid ammonia.) An example of proton transfer in the gas phase is the reaction of hydrogen chloride and ammonia gases. They produce the fine powder of ammonium chloride often seen coating surfaces in chemical laboratories (Fig. 10.5) ... 

Step 1 Write the chemical equation and Ka for the proton transfer equilibrium. Set up a table with columns labeled by the acid HA, H30+, and the conjugate base of the acid, A-. In the first row below the headings, show the initial concentration of each species. 

STRATEGY Because NH4+ is a weak acid and Cl- is neutral, we expect pH < 7. We treat the solution as that of a weak acid, using an equilibrium table as in Toolbox 10.1 to calculate the composition and hence the pH. First, write the chemical equation for proton transfer to water and the expression for Ca. Obtain the value of Ka from Kh for the conjugate base by using K, = KxJKh (Eq. 11a). The initial concentration of the acidic cation is equal to the concentration of the cation that the salt would produce if the salt were fully dissociated and the cation retained all its acidic protons. The initial concentrations of its conjugate base and H30+ are assumed to be zero. 

Although thermodynamics can be used to predict the direction and extent of chemical change, it does not tell us how the reaction takes place or how fast. We have seen that some spontaneous reactions—such as the decomposition of benzene into carbon and hydrogen—do not seem to proceed at all, whereas other reactions—such as proton transfer reactions—reach equilibrium very rapidly. In this chapter, we examine the intimate details of how reactions proceed, what determines their rates, and how to control those rates. The study of the rates of chemical reactions is called chemical kinetics. When studying thermodynamics, we consider only the initial and final states of a chemical process (its origin and destination) and ignore what happens between them (the journey itself, with all its obstacles). In chemical kinetics, we are interested only in the journey—the changes that take place in the course of reactions. 

H atom is attached to an N atom at the end of the chain), (hi If HN, is added to NH, a proton transfer reaction occurs. Wo the chemical equation for that reaction. 

Thus the reactant ions for chemical ionization formed in the methane plasma consists of approximately equal amounts of a strong gaseous Bronsted acid (CH5+) and ions which can act either as Lewis acids or Bronsted acids (C2H5+ + C3H5+). These reactant ions will effect the chemical ionization with an added substance by proton transfer or hydride ion transfer, both of which may be accompanied by fragmentation of the ion initially formed. 

We have previously shown (8) that the chemical ionization spectra using methane as reactant are generated by the combination of dissociative proton transfer from CH5 + and hydride ion abstraction and alkyl ion... 

The principles outlined above are, of course, important in electro-synthetic reactions. The pH of the electrolysis medium, however, also affects the occurrence and rate of proton transfers which follow the primary electron transfer and hence determine the stability of electrode intermediates to chemical reactions of further oxidation or reduction. These factors are well illustrated by the reduction at a mercury cathode of aryl alkyl ketones (Zuman et al., 1968). In acidic solution the ketone is protonated and reduces readily to a radical which may be reduced further only at more negative potentials. 

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