Isotopic substitution reaction

Another work (Russell and Light, 1971) was on tunnelling in isotopically substituted reaction of H + H2. It showed that tunnelling is determined, not only by the reaction-path height and width, but also by the curvature K(u) and the perpendicular vibrational frequency, which change from one isotopic reaction to another. 

Figure B3.4.1. The potential surface for the collinear D + H2 DH + H reaction (this potential is the same as for H + H2 H2 + H, but to make the products and reactants identification clearer the isotopically substituted reaction is used). The D + H2 reactant arrangement and the DH + H product arrangement are denoted. The coordinates are r, the H2 distance, and R, the distance between the D and the H2 centre of mass. Distances are measured in angstroms the potential contours shown are 4.7 eV,-4.55 eV,.. ., -3.8 eV. (The potential energy is zero when the particles are far from each other. Only the first few contours are shown.) For reference, the zero-point energy for H2 is -4.47 eV, i.e. 0.27 eV above the H2 potential minimum (-4.74 eV) the room-temperature thermal kinetic energy is approximately 0.03 eV. The graph uses the accurate Liu-Seigbahn-Truhlar-Horowitz (LSTH) potential surface [195).

Using the H-atom Rydberg tagging time-of-flight crossed molecular beam technique, Dr. Ren studied the reaction resonance and non-adiabatic effects at a full quantum resolved level in the F + H2 system. Through state-to-state resolved experiments, he provided the first conclusive evidence of reaction resonances in the F %,2) + H2 -> HF + H reaction. The dramatic difference between the dynamics for the F( P3/2) + H2(j = 0,1) reactions represents a textbook example of the role of reactant rotational level in resonance phenomena in this benchmark system. Dr. Ren has also carried out a very high-resolution experimental study on the dynamics of the isotope substituted reaction, F( P3/2) -I- HD -> HF -I- D, with spectroscopic accuracy (a few cm ). These findings provided a very clear physical picture for reaction resonances in this benchmark system, which has eluded us for more than 30 years. 

A special type of substituent effect which has proved veiy valuable in the study of reaction mechanisms is the replacement of an atom by one of its isotopes. Isotopic substitution most often involves replacing protium by deuterium (or tritium) but is applicable to nuclei other than hydrogen. The quantitative differences are largest, however, for hydrogen, because its isotopes have the largest relative mass differences. Isotopic substitution usually has no effect on the qualitative chemical reactivity of the substrate, but often has an easily measured effect on the rate at which reaction occurs. Let us consider how this modification of the rate arises. Initially, the discussion will concern primary kinetic isotope effects, those in which a bond to the isotopically substituted atom is broken in the rate-determining step. We will use C—H bonds as the specific topic of discussion, but the same concepts apply for other elements. 

Secondary isotope effects at the position have been especially thoroughly studied in nucleophilic substitution reactions. When carbocations are involved as intermediates, substantial /9-isotope effects are observed. This is because the hyperconjugative stabliliza-... 

Predict whether normal or inverse isotope effects will be observed for each reaction below. Explain. Indicate any reactions in which you would expect > 2. The isotopically substituted hydrogens are marked with asterisks. 

For the reactions given below, predict the effect on the rate of the isotope substitution which is described. Explain the basis of your prediction. 

Isotope effects are also useful in providing insight into other aspects of the mechanisms of individual electrophilic aromatic substitution reactions. In particular, because primary isotope effects are expected only when the breakdown of the c-complex to product is rate-determining, the observation of a substantial points to a rate-... 

Table 10.6. Kinetic Isotope Effects in Some Electrophilic Aromatic Substitution Reactions...

At this point, attention can be given to specific electrophilic substitution reactions. The kinds of data that have been especially useful for determining mechanistic details include linear ffee-energy relationships, kinetic studies, isotope effects, and selectivity patterns. In general, the basic questions that need to be asked about each mechanism are (1) What is the active electrophile (2) Which step in the general mechanism for electrophilic aromatic substitution is rate-determining (3) What are the orientation and selectivity patterns ... 

Consider a reactant molecule in which one atom is replaced by its isotope, for example, protium (H) by deuterium (D) or tritium (T), C by C, etc. The only change that has been made is in the mass of the nucleus, so that to a very good approximation the electronic structures of the two molecules are the same. This means that reaction will take place on the same potential energy surface for both molecules. Nevertheless, isotopic substitution can result in a rate change as a consequence of quantum effects. A rate change resulting from an isotopic substitution is called a kinetic isotope effect. Such effects can provide valuable insights into reaction mechanism. 

If the proton is not equidistant between A and B, it will undergo some movement in the symmetric stretching vibration. Isotopic substitution will, therefore, result in a change in transition state vibrational frequency, with the result that there will be a zero-point energy difference in the transition state. This will reduce the kinetic isotope effect below its maximal possible value. For this type of reaction, therefore, should be a maximum when the proton is midway between A and B in the transition state and should decrease as H lies closer to A or to B. 

Kinetic Isotope Effect. The change in reaction rate caused by isotopic substitution. 

Chemical kinetics is the study of the rates of chemical reactions. Its practice entails the measurement of concentrations as a function of time. These measurements are extended to other variables, such as the concentrations of additional species, pH, temperature, pressure, isotopic substitution, solvent, salt concentration, and so on. 

The route from kinetic data to reaction mechanism entails several steps. The first step is to convert the concentration-time measurements to a differential rate equation that gives the rate as a function of one or more concentrations. Chapters 2 through 4 have dealt with this aspect of the problem. Once the concentration dependences are defined, one interprets the rate law to reveal the family of reactions that constitute the reaction scheme. This is the subject of this chapter. Finally, one seeks a chemical interpretation of the steps in the scheme, to understand each contributing step in as much detail as possible. The effects of the solvent and other constituents (Chapter 9) the effects of substituents, isotopic substitution, and others (Chapter 10) and the effects of pressure and temperature (Chapter 7) all aid in the resolution. 

The [NiFe] hydrogenase from D. gigas has been used as a prototype of the [NiFe] hydrogenases. The enzyme is a heterodimer (62 and 26 kDa subunits) and contains four redox active centers one nickel site, one [3Fe-4S], and two [4Fe-4S] clusters, as proven by electron paramagnetic resonance (EPR) and Mosshauer spectroscopic studies (174). The enzyme has been isolated with different isotopic enrichments [6 Ni (I = I), = Ni (I = 0), Fe (I = 0), and Fe (I = )] and studied after reaction with H and D. Isotopic substitutions are valuable tools for spectroscopic assignments and catalytic studies (165, 166, 175). 

A disadvantage of this technique is that isotopic labeling can cause unwanted perturbations to the competition between pathways through kinetic isotope effects. Whereas the Born-Oppenheimer potential energy surfaces are not affected by isotopic substitution, rotational and vibrational levels become more closely spaced with substitution of heavier isotopes. Consequently, the rate of reaction in competing pathways will be modified somewhat compared to the unlabeled reaction. This effect scales approximately as the square root of the ratio of the isotopic masses, and will be most pronounced for deuterium or... 

In highly exothermic reactions such as this, that proceed over deep wells on the potential energy surface, sorting pathways by product state distributions is unlikely to be successful because there are too many opportunities for intramolecular vibrational redistribution to reshuffle energy among the fragments. A similar conclusion is likely as the total number of atoms increases. Therefore, isotopic substitution is a well-suited method for exploration of different pathways in such systems. 

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