Proton transfer, stepwise

We studied, at the B3LYP/6-31+G theoretical level, four monomers and 12 NH-pyrazole cyclamers, C-unsubstituted or bearing fluoro, chloro and bromo substituents at positions 3 and 5 [100], Two mechanisms of proton transfer, stepwise and synchronous, were calculated for dimers, trimers, and tetramers. The set of values of energies and geometries thus obtained provide useful insights about the dynamics of NH-pyrazoles in the solid state. It has been shown that pyrazole cyclamers exist not only in condensed phases but in the gas phase as well [101], thus our gas-phase calculations will provide information about the solid state. 

The double hydrogen bond in principle facilitates two mechanisms of double proton transfer stepwise and concerted. Studying the transfer rates within the semi-classical tunneling approximation of the variational transition state theory, Kim found that the two protons are transferred synchronously across the transition state with D2h symmetry [194], The actual proton-tunneling distance is considerably reduced due to the contraction of the hydrogen bonds, i.e., heavy atom motion promotes the proton transfer. On the other hand, the ab initio path-integral Car-Parinello calculations predict that the motion of the two protons in the vicinity of the potential minima is... 

On the other hand, it is clear that in the classical regime, T> (T i is the crossover temperature for stepwise transfer), the transition should be step-wise and occur through one of the saddle points. Therefore, there should exist another characteristic temperature. r 2> above which there exist two other two-dimensional tunneling paths with smaller action than that of the one-dimensional instanton. It is these trajectories that collapse to the saddle points atlT = T i. The existence of the second crossover temperature, 7, 2, for two-proton transfer has been noted by Dakhnovskii and Semenov [1989]. 

Isotope effect between the HH, HD, DH, and DD isotopomers was used as an important tool to determine the mechanism of the double-proton transfer. For concerted degenerate double-proton transfers in the absence of tunneling, the rule of the geometrical mean (RGM) should hold in good approximation, which states that /chh/ hd = /cdh/ dd-Tunneling may lead to a breakdown of this rule but the relation /chh > hd = dh > dd should remain valid. In the absence of secondary isotope effects the relation /chh HD = DH = 2 /cdd sliould liold for a stepwise pathway, even if tunneling is involved. 

With still further increase in concentration this process continues. In addition, we may mention that, although in the solutions discussed the H20 molecules outnumber the (H30)+ ions nearly ten to one, in the still more concentrated solutions the HaO molecules become more and more sparse. For indicators 6 to 17 the same stepwise procedure was followed in mixtures of H2SO4 and water and yielded progressively higher proton levels. With the last indicator, No. 17, measurements were made in mixtures containing from 96 to 100 per cent of H2SO4. In the 100 per cent H2SO4 the proton transfer presumably was... 

Phenylsulphine prepared in situ from phenylmethanesulphinyl chloride and triethyl-amine reacted with 1 -morpholinocyclohexene to form the addition product 169 having the enamine structure218. A similar experiment with phenylsulphine and 2-pyrrolidinocyclo-hexene gave only 2-phenylmethanesulphinyl cyclohexanone 170. The latter is most probably formed by hydrolysis of the corresponding enamine sulphoxide upon isolation. The reaction of sulphines with enamines is apparently a stepwise process involving the transient formation of the dipolar intermediate 171 which is stabilized by proton transfer, giving the enamine sulphoxide. 

Write the stepwise proton transfer equilibria for the deprotonation of (a) sulfuric acid, H2S04 (LA arsenic acid, H.As04 (c) phthalic acid. C6H4(COOH)2. 

Another key contribution of the Schwarz group was the recognition of the dramatic influence of oxide surfaces on bulk solution pH. In a landmark 1989 paper, Noh and Schwarz [7] demonstrated the method of mass titration, in which successive additions of oxide cause stepwise shifts in solution pH. This procedure is illustrated in Figure 6.7 [7], As indicated in Figure 6.1, the protonation-deprotonation chemistry of the surface hydroxyl groups is coupled to the liquid-phase pH. In mass titration, as the mass (or more appropriately, the surface area) of oxide in solution increases, the solution pH is brought to the PZC of the oxide, at which point no driving force for proton transfer exists... 

Polybrominated Biphenyls. The photolytic degradation of PBBs in solution has been the subject of several studies. Available data in the literature indicate that brominated biphenyls photodegrade by reduction in solvents capable of proton transfer with the formation of lower brominated biphenyls. For example, the irradiation of FireMaster BP-6 and 2,2, 4,4, 5,5 -hexabromobiphenyl in methanol at wavelengths >286 nm produced mainly penta- and tetrabromobiphenyl (Ruzo and Zabik 1975). FireMaster BP-6 photolyzed7 times faster than its chlorinated counterpart, 2,2, 4,4, 5,5 -hexachloro-biphenyl (Ruzo and Zabik 1975). Although an earlier study tentatively identified dimethoxy tetrabromobiphenyl as a photolysis product of FireMaster BP-6 (Ruzo and Zabik 1975), later work did not detect this compound (Ruzo et al. 1976). Earlier studies indicated that the debromination usually occurs with the stepwise preferential loss of bromine from the ortho and para positions of the biphenyl ring (i.e., 2, 2, 6, and 6 positions) (De Kok et al. 1977 Ruzo and Zabik 1975 Ruzo et al. 1976 Trotter 1977). Thus, the photolysis of 2,2, 4,4, 5,5 -hexachlorobiphenyl, the major component of FireMaster BP-6, would be expected to produce 23, 4,4, 5-pentabromobiphenyl and subsequently... 

Figure 8.2 Energy surface for addition of nucleophile Nuc to a carbonyl with concerted proton transfer from an acid HA. The lowest-energy path is indicated by the heavy line from point A to point B. Points C and D are the high-energy intermediates of the two possible stepwise paths. The circled point is the transition state.

In aqueous solution, proton transfer to tile first formed intermediate is very rapid. However, again for illustrating die stepwise changes that must occur on the way from reactants to products using curved-arrow notation, these steps are shown independently. 

The vertical electron affinity (EA) of acetone is given as —1.51 eV by Jordan and Burrow386. Lifshitz, Wu and Tiernan387 determine—among other compounds—the excitation function and rate constants of the slow proton transfer reactions between acclone-Ih, acetone-Dg and other ketones. The acetone enolate anion has been produced in a CO2 laser induced alkane elimination from alkoxide anions by Brauman and collaborators388-390. These show, e.g. that the methane elimination from t-butoxide anion is a stepwise process ... 

DFT calculations were performed for the double proton transfer in bicyclic 2,2 -bis(4,5,6,7-tetrahydro-l,3-diazepine) (Figure 8) <2001CPL591>. Both a concerted and a stepwise mechanism for proton transfer are considered. Though the concerted transition state has two imaginary eigenfrequencies, dynamical calculations have demonstrated that it has to be taken into account in the mechanism of the proton transfer even if it is not a true reaction path. 

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