Spectator mechanism

The preassociation mechanism is more efficient than the trapping mechanism because it generates an intermediate which immediately reacts by an ultrafast proton transfer (in the pre-association complex, Int) and thus avoids the diffusion-controlled step bringing the catalyst and intermediate together. This mechanism is sometimes called a spectator mechanism because, although the catalyst is present in the transition structure, it is not undergoing any transformation [10]. 

See also microscopic diffusion control spectator mechanism. 

The formation of B from A may itself be a bimolecular reaction with some other reagent. Since C does not assist the formation of A, it is described as being present as a spectator, and hence such a mechanism is sometimes referred to as a spectator mechanism. 

Deducing ionic equations from observed chemical changes, not by mechanically cancelling out spectator ions in chemical equations. 

In either case, abstraction mechanisms are direct (no long-lived collision complex is formed), have small entropy costs ( loose transition states), and typically deposit large amounts of vibrational energy in the newly formed bond while the other bonds in the system act largely as spectators. 

A close analogy to the localized surface interaction can be found in the field of chemical kinetics, namely, in the spectator stripping mechanism (5, 6) of the gas reactions, as evidenced by the recent crossed-molecular-beams experiments. Here the projectile seems to meet with only a part of the target molecule (that one to be transferred), while the rest of the target behaves as a spectator, in a sense not taking part in the reaction. 

B—All substances involved, directly or indirectly, in the rate-determining step will change the rate when their concentrations are changed. The ion is required in the balanced chemical equation, so it cannot be a spectator ion, and it must appear in the mechanism. Catalysts will change the rate of a reaction. Since H does not affect the rate, the reaction is zero order with respect to this ion. 

It is evident from the preceding discussion that some, but not all, reaction mechanisms are sensitive to the level of solvation present. What of the counterion, the. oppositely charged ion in solution often regarded merely as a spectator In ICR spectrometry, only one type of ion, positive or negative, is normally trapped in the cell at a time. The chemistry of ions independent of any counterion can thus be examined. 

From the temperature variation of the equilibrium constant, thermodynamic parameters for the reaction were also obtained. The extent of formation of [Mo(CO)5l]" was found to be cation-dependent, and while equilibrium constants of 39 and 21 atm L moF were obtained for Bu4P and pyH+, none of the anionic iodide complex was observed for Na. Despite this variation, there seemed to be no correlation between the concentration of [Mo(CO)5l]" and the rate of the catalytic carbonylation reaction. It was proposed that [Mo(CO)5] and [Mo(CO)5l] are spectator species, with the catalysis being initiated by [Mo(CO)5]. Based on the in situ spectroscopic results and kinetic data, a catalytic mechanism was suggested, involving radicals formed by inner sphere electron transfer between EtI and [Mo(CO)5]. 

Ions such as sodium, Na% potassium, K% and lithium, Lh, are usually spectator ions and therefore aren t part of the reaction mechanism. 

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