Turnover catalysis

Earlier work in this field has been thoroughly reviewed [1,2]. However, to illustrate in a sensible and logical way the evolution from simple metal ion promotion of acyl transfer in supramolecular complexes to supramolecular catalysts capable of turnover catalysis, an account of earlier work is appropriate. The following sections present a brief overview of our earlier observations related to the influence of alkaline-earth metal ions and their complexes with crown ethers on the alcoholysis of esters and of activated amides under basic conditions. 

As a variation on the theme, instead of a zinc(II)-salophen unit, receptor 9 features a 2-pyridone unit, that is a known bifunctional catalyst for the rate limiting breakdown of the tetrahedral intermediate involved in the aminolysis of active esters in aprotic solvents. Turnover catalysis was indeed observed when the reaction between propylamine and PNPCC (Equation 8.5) was carried out in CH2CI2/CH3CN 99 1 in the presence of receptor 9. It was estimated that the reaction inside 9 is ca. 6000 times faster than the reaction in the bulk solvent. 

More recently, we have extended ion pairing to template-directed chlorination [15]. Since in the chlorination reactions HCl is produced, we could not use carboxyl-ate anions. However, ion pairs of substrate cations with iodoaryl templates carrying sulfonate anion groups directed chlorination with reasonably good selectivity. Somewhat poorer selectivity, because of flexibility, was achieved when the template carried the cationic group and the substrate was a sulfate anion. The ion paired template shows turnover catalysis by moving on to another substrate molecule after... 

Cyclodextrin dimers have been prepared with a linker that can cany a metal ion next to an ester group of a bound substrate. Very large rates of hydrolysis—and good turnover catalysis—are seen in some examples. 

In order for the cyclooxygenase to function, a source of hydroperoxide (R—O—O—H) appears to be required. The hydroperoxide oxidizes a heme prosthetic group at the peroxidase active site of PGH synthase. This in turn leads to the oxidation of a tyrosine residue producing a tyrosine radical which is apparendy involved in the abstraction of the 13-pro-(5)-hydrogen of AA (25). The cyclooxygenase is inactivated during catalysis by the nonproductive breakdown of an active enzyme intermediate. This suicide inactivation occurs, on average, every 1400 catalytic turnovers. 

An artificial metalloenzyme (26) was designed by Breslow et al. 24). It was the first example of a complete artificial enzyme, having a substrate binding cyclodextrin cavity and a Ni2+ ion-chelated nucleophilic group for catalysis. Metalloenzyme (26) behaves a real catalyst, exhibiting turnover, and enhances the rate of hydrolysis of p-nitrophenyl acetate more than 103 fold. The catalytic group of 26 is a -Ni2+ complex which itself is active toward the substrate 1, but not toward such a substrate having no metal ion affinity at a low catalyst concentration. It is appearent that the metal ion in 26 activates the oximate anion by chelation, but not the substrate directly as believed in carboxypeptidase. 

The mechanistic investigations presented in this section have stimulated research directed to the development of advanced ruthenium precatalysts for olefin metathesis. It was pointed out by Grubbs et al. that the utility of a catalyst is determined by the ratio of catalysis to the rate of decomposition [31]. The decomposition of ruthenium methylidene complexes, which attribute to approximately 95% of the turnover, proceeds monomolecularly, which explains the commonly observed problem that slowly reacting substrates require high catalyst loadings [31]. This problem has been addressed by the development of a novel class of ruthenium precatalysts, the so-called second-generation catalysts. 

Figure 2.3. Catalysis (0), classical promotion ( ), electrochemical promotion ( , ) and electrochemical promotion of a classically promoted (sodium doped) ( , ) Rh catalyst deposited on YSZ during NO reduction by CO in presence of gaseous 02.14 The Figure shows the temperature dependence of the catalytic rates and turnover frequencies of C02 (a) and N2 (b) formation under open-circuit (o.c.) conditions and upon application (via a potentiostat) of catalyst potential values, UWr, of+1 and -IV. Reprinted with permission from Elsevier Science.

In the early days of catalysis the porous high surface area support was usually thought to be inert. It soon became obvious, however, that the catalytic activity, or turnover frequency, of a catalytic reaction on a given active phase is quite often seriously affected both by the crystallite size and by the material of the support. 

As discussed before, very high turnover numbers of the catalytic site and a large active electrode area are the most important features for effective catalysis. In the following sections three relatively successful approaches are illustrated in detail, all of which make use of one or both of these parameters. A further section will deal with non-redox modified electrodes for selectivity enhancement of follow-up reactions. 

Before deriving the rate equations, we first need to think about the dimensions of the rates. As heterogeneous catalysis involves reactants and products in the three-dimensional space of gases or liquids, but with intermediates on a two-dimensional surface we cannot simply use concentrations as in the case of uncatalyzed reactions. Our choice throughout this book will be to express the macroscopic rate of a catalytic reaction in moles per unit of time. In addition, we will use the microscopic concept of turnover frequency, defined as the number of molecules converted per active site and per unit of time. The macroscopic rate can be seen as a characteristic activity per weight or per volume unit of catalyst in all its complexity with regard to shape, composition, etc., whereas the turnover frequency is a measure of the intrinsic activity of a catalytic site. 

The Holy Grail of catalysis has been to identify what Taylor described as the active site that is, that ensemble of atoms which is responsible for the surface reactions involved in catalytic turnover. With the advent of atomically resolving techniques such as scanning tunnelling microscopy it is now possible to identify reaction centres on planar surfaces. This gives a greater insight also into reaction kinetics and mechanisms in catalysis. In this paper two examples of such work are described, namely CO oxidation on a Rh(llO) crystal and methanol selective oxidation to formaldehyde on Cu(llO). 

Attempts to determine how the activity of the catalyst (or the selectivity which is, in a rough approximation, the ratio of reaction rates) depends upon the metal particle size have been undertaken for many decades. In 1962, one of the most important figures in catalysis research, M. Boudart, proposed a definition for structure sensitivity [4,5]. A heterogeneously catalyzed reaction is considered to be structure sensitive if its rate, referred to the number of active sites and, thus, expressed as turnover-frequency (TOF), depends on the particle size of the active component or a specific crystallographic orientation of the exposed catalyst surface. Boudart later expanded this model proposing that structure sensitivity is related to the number of (metal surface) atoms to which a crucial reaction intermediate is bound [6]. 

Important inherent characteristics of an enzyme that should be considered are the substrate affinity, characterized by the Michaelis constant the rate of turnover fecat> providing the catalytic efficiency fecat/ M. and the catalytic potential. Several attempts to compare enzyme catalysis with that of platinum have been published. Direct comparisons are difficult, because enzyme electrodes must be operated in aqueous electrolyte containing dissolved substrate, whereas precious metal electrodes aie often supplied with a humidified gaseous stream of fuel or oxidant, and produce water as steam. It is not straightforward to compare tme optimal turnover rates per active site, as it is often unclear how many active sites are being engaged in a film of enzyme on an electrode. 

The shape of the hydrogenase catalytic voltammograms shown in Fig. 17.14 also changes as the temperamre is raised. At 10 °C, the current tends towards a plateau at high overpotential as catalysis becomes limited by the inherent turnover frequency of the enzyme, but at higher temperamres, the current continues to increase linearly with electrochemical driving force. This has been attributed to a range of different... 

The half-wave potentials of (FTF4)Co2-mediated O2 reduction at pH 0-3 shifts by — 60 mV/pH [Durand et ah, 1983], which indicates that the turnover-determining part of the catalytic cycle contains a reversible electron transfer (ET) and a protonation, or two reversible ETs and two protonation steps. In contrast, if an irreversible ET step were present, the pH gradient would be 60/( + a) mV/pH, where n is the number of electrons transferred in redox equilibria prior to the irreversible ET and a is the transfer coefficient of the irreversible ET. The —60 mV/pH slope is identical to that manifested by simple Ee porphyrins (see Section 18.4.1). The turnover rate of ORR catalysis by (ETE4)Co2 was reported to be proportional to the bulk O2 concentration [Collman et ah, 1994], suggesting that the catalyst is not saturated with O2. 

So far, certain biomimetic catalysts (1 and 2b in Fig. 18.17) have been shown to reduce O2 to H2O under a slow electron flux at physiologically relevant conditions (pH 7,0.2-0.05 V potential vs. NHE) and retain their catalytic activity for >10" turnovers. Probably, only the increased stability of the turning-over catalyst is of relevance to the development of practical ORR catalysts for fuel cells. In addition, biomimetic catalysts of series 1,2,3, and 5, and catalyst 4b are the only metalloporphyrins studied in ORR catalysis with well-defined proximal and distal environments. For series 2, which is by far the most thoroughly studied series of biomimetic ORR catalysts, these well-defined environments result in an effective catalysis that seems to be the least sensitive among all metalloporphyrins to the electrode material (whether the catalyst is adsorbed or in the film) and to chemicals present in the electrolyte or in the O2 stream, including typical catalyst poisons (CO and CN ). 

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