Reverse protonation

Chemical off—on switching of the chemiluminescence of a 1,2-dioxetane (9-benzyhdene-10-methylacridan-l,2-dioxetane [66762-83-2] (9)) was first described in 1980 (33). No chemiluminescence was observed when excess acetic acid was added to (9) but chemiluminescence was recovered when triethylamine was added. The off—on switching was attributed to reversible protonation of the nitrogen lone pair and modulation of chemically induced electron-exchange luminescence (CIEEL). Base-induced decomposition of a 1,2-dioxetane of 2-phen5l-3-(4 -hydroxyphenyl)-l,4-dioxetane (10) by deprotonation of the phenoHc hydroxy group has also been described (34). 

C6Hg)2] is reversibly protonated by dilute acids to give [W(p6-C6H6)2H]+. 

A direct irreversible proton transfer in limiting stage of 1-ethoxybut- l-en-3-yne hydration is confirmed by the value of kinetic isotopic effect k ilk = 2.9. For fast reversible proton transitions this value is less than 1. 

Another similarity with water is that alcohols and phenols are both weakly basic and weaJkly acidic. As weak bases, they are reversibly protonated by strong acids to yield oxonium ions, TOFty. ... 

Rate parameters [(da/df), A, E measured for dehydroxylations are frequently sensitive to the availability of water vapour in the vicinity of the reactant and this accounts for the apparent variations in kinetic data sometimes found between different reports concerned with the same reaction. Water adsorbed on product adjoining the reaction interface could be expected to participate in the reversible proton transfer step, the precursor to water elimination. Despite this influence of PH2o on reaction rate, we are aware of no reported instance of S—T behaviour in dehydroxylations. 

Also considered as possibilities have been transition states involving IV, below, the conjugate base of II, and either RjNHJ or BH+ 29,30. This mechanism, with II and IV maintained at equilibrium by rapid, reversible proton transfers and BH + or R2NH2 assisting separation of the leaving group from intermediate IV in the rate-limiting step, may be formulated as... 

These kinetic results are consistent with a fast reversible protonation of the nitrosamine followed by a unimolecular decomposition, viz. 

Tetraene 4 (Scheme 1.3), when treated with 40 mol % of triflic acid in methylene chloride at -23 °C for 1 h, gives the adducts 5 and 6 in a 1 1 ratio as the main reaction products. The formation of these adducts has been justified [21] by a stepwise mechanism that requires an initial reversible protonation of 4 to produce the allyl cation 7, which then cyclizes to 8 and 9 in a non-reversible process. Deprotonation of 8 and 9 gives 5 and 6, respectively. 

Using an electron-gun source, tungsten atoms were reacted with benzene, toluene, or mesitylene at 77 K, to form the expected (arene)2W complex (42) in a yield of 30%, compared with the —2% yield from the previously published, bis(benzene)W synthesis (32). These arene complexes are reversibly protonated, to give the appropriate [(T7-arene)2WH] species. By using the same technique, the analogous, niobium complexes were isolated (43). 

The phosphorimide (44) hydrolyses in aqueous solution to the phos-phoramidate (45) and the rate dependence is well represented on the basis of a reversible protonation (pAa 6.4) followed by rate-determining formation of products. However, studies in H2 0 indicate that the molar incorporation of in the product varies from 0.22 at pH 4 to 0.81 at... 

The basicities of some phosphinamides (84) have been measured and the acid-catalysed hydrolysis studied. Unsubstituted and A -alkyl derivatives follow an A2 mechanism of reversible protonation followed by ratedetermining water attack. However, the rates for the A -aryl derivatives follow Hq (but with a slope of 0.5), and an A mechanism was suggested as most consistent with this fact and the solvent isotope effect. The anomalous dependence on Ho, together with the large negative value of A5, while not necessarily excluding an ionization mechanism, leaves the question in some doubt. 

The equilibrium ratios of enolates for several ketone-enolate systems are also shown in Scheme 1.1. Equilibrium among the various enolates of a ketone can be established by the presence of an excess of ketone, which permits reversible proton transfer. Equilibration is also favored by the presence of dissociating additives such as HMPA. The composition of the equilibrium enolate mixture is usually more closely balanced than for kinetically controlled conditions. In general, the more highly substituted enolate is the preferred isomer, but if the alkyl groups are sufficiently branched as to interfere with solvation, there can be exceptions. This factor, along with CH3/CH3 steric repulsion, presumably accounts for the stability of the less-substituted enolate from 3-methyl-2-butanone (Entry 3). 

By analogy with acids above, specific basic catalysis is found to be characteristic of reactions in which there is rapid, reversible proton-removal from the substrate before the slow, rate-limiting step. 

We would expect the C=0 linkage, by analogy with C=C (p. 178), to undergo addition reactions but whereas polar attack on the latter is normally initiated only by electrophiles, attack on the former— because of its bipolar nature—could be initiated either by electrophilic attack of X or X on oxygen or by nucleophilic attack of Y or Yt on carbon (radical-induced addition reactions of carbonyl compounds are rare). In practice, initial electrophilic attack on oxygen is of little significance except where the electrophile is an acid (or a Lewis acid), when rapid, reversible protonation may be a prelude to slow, rate-limiting attack by a nucleophile on carbon, to complete the addition, i.e. the addition is then acid-catalysed. 

Brewer WE, Martinez ML, Chou PT (1990) Mechanism of the ground-state reverse proton transfer of 2-(2-hydroxyphenyl)benzothiazole. J Phys Chem 94 1915-1918... 

The osmium formimidoyl 16 is reversibly protonated to a secondary carbene complex (44) ... 

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.

---