Lifetime, active complex transition structure

If the reaction is considered on the molar scale, the activated complexes are the molecular species at the hypothetical free energy maximum which separates reactant and product molecules. The distinction between an activated complex (transition structure), which is a real molecular species, though of exceedingly short lifetime, and transition state, which is a hypothetical thermodynamic state on the molar scale, is important though frequently confused [7]. 

This then is the dilemma. The activated complex occurs at the transition state and has a vanishingly short lifetime ( 1 bond vibration or 10 13 sec) yet its structure and energy must be described and changes in its structure and energy must be evaluated if we are to compare different reactants in a predictive way. 

A variety of techniques have been applied to investigate enzyme reaction mechanisms. Kinetic and X-ray crystallographic studies have made major contributions to the elucidation of enzyme mechanisms. Valuable information has been gained from chanical, spectroscopic and biochemical studies of the transition-state structures and intermediates of enzyme catalysis. Computational studies provide necessary refinement toward our understanding of enzyme mechanisms. The ability of an enzyme to accelerate the rate of a chemical reaction derives from the complementarity of the enzyme s active site structure to the activated complex. The transition state by definition has a very short lifetime ( 10 s). Stabilization of the transition state alone is necessary but not sufficient to give catalysis, which requires differential binding of substrate and transition state. Thus a detailed enzyme reaction mechanism can be proposed only when kinetic, chemical and structural components have been studied. The online enzyme catalytic mechanism database is accessible at EzCatDB (http //mbs.cbrc.jp/EzCatDB/). 

No catalyst has an infinite lifetime. The accepted view of a catalytic cycle is that it proceeds via a series of reactive species, be they transient transition state type structures or relatively more stable intermediates. Reaction of such intermediates with either excess ligand or substrate can give rise to very stable complexes that are kinetically incompetent of sustaining catalysis. The textbook example of this is triphenylphosphine modified rhodium hydroformylation, where a plot of activity versus ligand metal ratio shows the classical volcano plot whereby activity reaches a peak at a certain ratio but then falls off rapidly in the presence of excess phosphine, see Figure... 

Transition metal catalysts, specifically those composed of iron nanoparticles, are widely employed in industrial chemical production and pollution abatement applications [67], Iron also plays a cracial role in many important biological processes. Iron oxides are economical alternatives to more costly catalysts and show activity for the oxidation of methane [68], conversion of carbon monoxide to carbon dioxide [58], and the transformation of various hydrocarbons [69,70]. In addition, iron oxides have good catalytic lifetimes and are resistant to high concentrations of moisture and CO which often poison other catalysts [71]. Li et al. have observed that nanosized iron oxides are highly active for CO oxidation at low tanperatures [58]. Iron is unique and more active than other catalyst and support materials because it is easily reduced and provides a large number of potential active sites because of its highly disordered and defect rich structure [72, 73]. Previous gas-phase smdies of cationic iron clusters have included determination of the thermochemistry and bond energies of iron cluster oxides and iron carbonyl complexes by Armentrout and co-workers [74, 75], and a classification of the dissociation patterns of small iron oxide cluster cations by Schwarz et al. [76]. 

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