Metal site reaction

A selective method for benzylic metalation of o-, m-, and p-substituted toluenes has been reported using BuLi/f-BuOKVTMP and rationalized by the ability of the mixed metal amide base to facilitate an anion migration from the kinetic (o-aryl) to the benzylic metalation site. Reaction of 2-(l-phenylethylidene)malononitrile and 2,2,2-trifluoro-1 -phenylethanone gives (2 ,4 )-2-cyano-6,6,6-trifluoro-3,5-diphenyl-hexa-2,4-dienamide via a vinylogous aldol reaction followed by rearrangement of the 2/f-pyran intermediate (Scheme 52). °°... 

The passive state of a metal can, under certain circumstances, be prone to localized instabilities. Most investigated is the case of localized dissolution events on oxide-passivated surfaces [51, 106, 107, 108, 109, 110, ill, 112, 113, 114, 115, 116, 117 and 118]. The essence of localized corrosion is that distinct anodic sites on the surface can be identified where the metal oxidation reaction (e.g. Fe —> Fe + 2e ) dominates, surrounded by a cathodic zone where the reduction reaction takes place (e.g. 2Fi + 2e —> Fi2). The result is the fonnation of an active pit in the metal, an example of which is illustrated in figure C2.8.6(a) and (b). 

Fig. 9. Corrosion model of silver development. As the haUde ion, X, is removed into solution at the etch pit, the silver ion,, travels interstitiaHy, Ag/ to the site of the latent image where it is converted to silver metal by reaction with the color developer, Dev. Dev represents oxidized developer.

Fig. 9. Catalyst pore and reaction. The CO diffuses into a precious metal site D reacts with O2 and leaves as CO2.

Azaferrocene reacts with aromatic hydrocarbons in the presence of aluminium chloride, giving rise to the cationic complexes of the type (Ti -arene)(Ti -cyclopenta-dienyl)iron(l+) isolated as BF4 salts [87JOM(333)71]. The complex 28 is obtained by reaction of the sulfane compound [Cp(SMc2)3Fe]BF4 with pentamethyl-pyrrole [88AG(E)579 88AG(E)1468 90ICA(170)155]. The metallic site in this center reveals expressed Lewis acidity (89CB1891). 

The mechanism through which catalytic metal carbene reactions occur is outlined in Scheme 2. With dirhodium(II) catalysts the open axial coordination site on each rhodium serves as the Lewis acid center that undergoes electrophilic addition to the diazo compound. Lewis bases that can occupy the axial coor-... 

The use of direct electrochemical methods (cyclic voltammetry Pig. 17) has enabled us to measure the thermodynamic parameters of isolated water-soluble fragments of the Rieske proteins of various bci complexes (Table XII)). (55, 92). The values determined for the standard reaction entropy, AS°, for both the mitochondrial and the bacterial Rieske fragments are similar to values obtained for water-soluble cytochromes they are more negative than values measured for other electron transfer proteins (93). Large negative values of AS° have been correlated with a less exposed metal site (93). However, this is opposite to what is observed in Rieske proteins, since the cluster appears to be less exposed in Rieske-type ferredoxins that show less negative values of AS° (see Section V,B). 

There are reports (reviewed in Ref. (55)) of acetylene reduction by FeMoco using very powerful reductants such as sodium borohydride or sodium amalgam. Unfortunately, in most of these experiments the integrity of FeMoco after reaction was not established, and thus the reaction could have been carried out by fragments of FeMoco. Reduction of acetylene bound to a metal site by powerful reductants is well established. 

Another SBU with open metal sites is the tri-p-oxo carboxylate cluster (see Section 4.2.2 and Figure 4.2). The tri-p-oxo Fe " clusters in MIL-100 are able to catalyze Friedel-Crafts benzylation reactions [44]. The tri-p-oxo Cr " clusters of MIL-101 are active for the cyanosilylation of benzaldehyde. This reaction is a popular test reaction in the MOF Hterature as a probe for catalytic activity an example has already been given above for [Cu3(BTC)2] [15]. In fact, the very first demonstration of the catalytic potential of MOFs had aheady been given in 1994 for a two-dimensional Cd bipyridine lattice that catalyzes the cyanosilylation of aldehydes [56]. A continuation of this work in 2004 for reactions with imines showed that the hydrophobic surroundings of the framework enhance the reaction in comparison with homogeneous Cd(pyridine) complexes [57]. The activity of MIL-lOl(Cr) is much higher than that of the Cd lattices, but in subsequent reaction rans the activity decreases [58]. A MOF with two different types of open Mn sites with pores of 7 and 10 A catalyzes the cyanosilylation of aromatic aldehydes and ketones with a remarkable reactant shape selectivity. This MOF also catalyzes the more demanding Mukaiyama-aldol reaction [59]. 

The principle introduced above is best exploited by classifying lanthanide compounds not by oxidation state, but by the number of 4f electrons at the metal site. For example, the reaction... 

In 1990, Schroder and Schwarz reported that gas-phase FeO" " directly converts methane to methanol under thermal conditions [21]. The reaction is efficient, occuring at 20% of the collision rate, and is quite selective, producing methanol 40% of the time (FeOH+ + CH3 is the other major product). More recent experiments have shown that NiO and PtO also convert methane to methanol with good efficiency and selectivity [134]. Reactions of gas-phase transition metal oxides with methane thus provide a simple model system for the direct conversion of methane to methanol. These systems capture the essential chemistry, but do not have complicating contributions from solvent molecules, ligands, or multiple metal sites that are present in condensed-phase systems. 

Although much progress has been made toward understanding the nature and probable catalytic behavior of active sites on CoMo/alumlna catalysts, much obviously remains to be accomplished. Detailed explanation of the acidic character of the reduced metal sites evidently most important In HDS, and presumably In related reactions, must await the Increased understanding which should come from studies of simplified model catalysts using advanced surface science techniques. Further progress of an Immediately useful nature seems possible from additional Infrared study of the variations produced In the exposed metal sites as a result of variations In preparation, pretreatment, and reaction conditions. 

The activity and stability of catalysts for methane-carbon dioxide reforming depend subtly upon the support and the active metal. Methane decomposes to carbon and hydrogen, forming carbon on the oxide support and the metal. Carbon on the metal is reactive and can be oxidized to CO by oxygen from dissociatively adsorbed COj. For noble metals this reaction is fast, leading to low coke accumulation on the metal particles The rate of carbon formation on the support is proportional to the concentration of Lewis acid sites. This carbon is non reactive and may cover the Pt particles causing catalyst deactivation. Hence, the combination of Pt with a support low in acid sites, such as ZrO, is well suited for long term stable operation. For non-noble metals such as Ni, the rate of CH4 dissociation exceeds the rate of oxidation drastically and carbon forms rapidly on the metal in the form of filaments. The rate of carbon filament formation is proportional to the particle size of Ni Below a critical Ni particle size (d<2 nm), formation of carbon slowed down dramatically Well dispersed Ni supported on ZrO is thus a viable alternative to the noble metal based materials. 

Methane reforming with carbon dioxide proceeds in a complex sequence of reaction steps involving the dissociative adsorption/reaction of methane and COj at metal sites. Hydrogen is generated during methane dissociation In the second set of reactions CO2 dissociates into CO and adsorbed oxygen. The reaction between the surface bound carbon (from methane dissociation) and the adsorbed oxygen (from CO2 dissociation ) yields carbon monoxide. A stable catalyst can only be achieved if the two sets of reactions are balanced. 

As is well documented, formation of chemisorbed oxygen species on a Pt surface at V > 0.75 V occurs in an inert atmosphere on Pt in contact with an aqueous, or hydrous polymer electrolyte, by anodic discharge of water molecules to form OHads on metal sites, according to the Reaction (1.3). It is this chemisorbed oxygen species, derived from water discharge, that will be considered in the following discussion. Significantly, the Reaction (1.3) is associated with a redox potential K(H20)/Pt-OHads which is quite different from the redox potential for the faradaic ORR process,... 

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