Heterolytic exchange

In the absence of exchange with the catalyst (heterolytic exchange), the rate of homolytic exchange is given by... 

When exchange with lattice oxygen takes place (heterolytic exchange), the kinetic equations become more complicated. The overall fraction of in the gas phase (a) decreases, i.e. da/dr is negative. The kinetic data can be represented by the following equation... 

Cunningham and co-workersl have monitored the atomic fraction 18 ( fa) to distinguish the homomolecular and heterolytic exchange processes ... 

Studies of the homomolecular and heterolytic exchange processes are generally in the form of the measurement of rates under isothermal conditions. However, studies have also been made of temperature programmed isotopic exchange, in which the oxide is subjected to a temperature ramp under the reaction atmosphere, and the partial pressures of various isotopic oxygen species is determined as a function of temperature (e.g., Refs. 20-21). The photoactivation of oxygen exchange has also been reported in a number of studies which have been performed under UV irradiation (e.g.. Refs. 18, 22, 23). 

Comparison of zinc alkoxide and zinc hydroxide bond energies has been made. The relative heterolytic bond energies for hydroxide, methoxide, ethoxide, and tert-butoxide were determined from studies of a series of alkoxide exchange equilibria using a four-coordinate monomeric zinc tris(pyrazolyl)borate compound.335... 

The products of reductive cyclization incorporate two non-exchangeable hydrogen atoms. Homolytic and heterolytic hydrogen activation pathways may now be discriminated on the basis of hydrogen-deuterium crossover experiments. Reductive cyclization of the indicated nitrogen-tethered enyne under a mixed atmosphere... 

The ESR signal due to 02 demonstrates that the heterolytic activation of R-H has occurred. An interesting feature of the H-D exchange reactions over the MgO surface is the low activation energy, i.e., Ea 2 kcal/mol. This is lower than the gas phase for the reaction H + D2 —> 2 D + HD. The high activity of the ionic oxides has been attributed to the presence of basic sites and in particular to defect sites that are formed during the oxide preparation that persist even at elevated temperatures.41 42... 

In the early nineteen-sixties Halpem, James and co-workers studied the hydrogenation of water-soluble substrates in aqueous solutions catalyzed by rathenium salts [6]. RuCh in 3 M HCl catalyzed the hydrogenation of Fe(III) to Fe(II) at 80 °C and 0.6 bar H2. Similarly, Ru(IV) was autocatalytically reduced to Ru(III) which, however, did not react further. An extensive study of the effect of HCl concentration on the rate of such hydrogenations revealed, that the hydrolysis product, [RuCln(OH)(H20)5. ] " was a catalyst of lower activity. It was also established, that the mechanism involved a heterolytic splitting of H2. In accordance with this suggestion, in the absence of reducible substrates, such as Fe(in) there was an extensive isotope exchange between the solvent H2O and D2 in the gas phase. 

The general observation in the published work has been that for species such as hexamminechromium, thiocyanatopentammine, or the hexa-aquo ion where O18 exchange was looked at, irradiation produced a substitution reaction and nothing else. Moreover the reaction mode was independent of wave length, and the quantum yields did not change much. From a morphological point of view, there are essentially three types of explanations. First all excited states independently lead to the same chemical sequence, and we suppose that the primary act is simply a heterolytic bond fission. 

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