Metal complexes, adsorption adsorbed

In spite of these limitations, three examples of (salen)-metal complex adsorption have been described. In the first one, Jacobsen s complex (la-MnCl) was adsorbed on Al-MCM-41 [27] by impregnation with a solution of the complex in dichloromethane, an approach that prevents the possible cationic exchange. The results in the epoxidation of 1,2-dihydronaphthalene with aqueous NaOCl were comparable to those obtained in solution, with only a slight reduction in enantioselectivity (55% ee instead of 60% ee). However, recycling of this catalyst was not described. 

Metal-complex adsorption can directly lead to surface reaction, as has been observed recently for cobalt ammine complexes adsorbing over carbon substrates [41, 42]. The uptake of cobalt hexaammine (CoHA), [(NH3)6Co]+3... 

Figure 8 shows the preliminary results from our laboratory for selective adsorption of sulfur compounds from a commercial diesel fuel using a transition metal complex based adsorbent A-1. Figure 9 shows the corresponding results for a model diesel fuel that contains naphthalene, 2-methylnaphthalene, DBF and 4,6-DMDBT. Based on the computational and experimental results, it is theoretically possible and experimentally doable to distinguish between sulfur compounds and aromatic compounds in diesel fuels using a solid adsorbent. 

Instead of electrostatic (or physical) adsorption, metal uptake onto oxides might be considered chemical in nature. In chemical mechanisms, the metal precursor is envisioned to react with the oxide surface, involving as surface-ligand exchange [13,14] in which OH groups from the surface replace ligands in the adsorbing metal complex. In this section it will be shown that a relatively simple electrostatic interpretation of the adsorption of a number of catalyst precursors is the most reasonable one for a number of noble metal/oxide systems. 

The surface morphologies of PAMAM dendrimers have been studied extensively by Turro and co-workers [16-23]. As shown in Scheme 4, one approach was to study the adsorption of organic dye molecules and metal complexes on the dendrimer surface by UY-Vis and fluorescence spectroscopy another approach took advantages of electron transfer processes between two adsorbed species on a single dendrimer surface or between the adsorbed species on a dendrimer surface and other species in aqueous solution. 

Organic material can strongly adsorb metal ions the functional groups on their surfaces act as ligands (carboxyl, amino groups etc.) for metal ions. All these functional groups favor the surface complex formation with metals the adsorption reactions are favored at higher pH (Fig. 11.11). 

Metal Ion Adsorption in Mixtures of Multiple Solid Phases. One of the arguments put forth for extending the concepts of solution coordination chemistry to heterogeneous systems is the hypothesis that the mineral components of soils or sediments can be considered as ligands which compete for complexation of adsorbates. To this end, it is important to know the relative ability of different mineral surfaces to complex solutes. 

The adsorption of transition metal complexes by minerals is often followed by reactions which change the coordination environment around the metal ion. Thus in the adsorption of hexaamminechromium(III) and tris(ethylenediamine) chromium(III) by chlorite, illite and kaolinite, XPS showed that hydrolysis reactions occurred, leading to the formation of aqua complexes (67). In a similar manner, dehydration of hexaaraminecobalt(III) and chloropentaamminecobalt(III) adsorbed on montmorillonite led to the formation of cobalt(II) hydroxide and ammonium ions (68), the reaction being conveniently followed by the IR absorbance of the ammonium ions. Demetallation of complexes can also occur, as in the case of dehydration of tin tetra(4-pyridyl) porphyrin adsorbed on Na hectorite (69). The reaction, which was observed using UV-visible and luminescence spectroscopy, was reversible indicating that the Sn(IV) cation and porphyrin anion remained close to one another after destruction of the complex. 

If the anodic anion transfer (anionic adsorption, Eqn. 9-13a) to form an adsorbed metallic ion complex is the rate-determining step, the Tafel constant, a = 1 - p, win be obtained from Eqn. 9-14. If the anodic transfer of the adsorbed metallic ion complex (desorption of complexes, Eqn. 9-13b) is the rate-determining step, the Tafel constant, a = 2 - p, will be obtained from Eqns. 9-16 and 9-17. Similarly, if the cathodic anion transfer (anionic desorption, Eqn. 9-13a) is determining the rate, the Tafel constant in the cathodic reaction, a = 1 p, will be obtained from Eqns. 9-15 and 9-16 and if the cathodic transfer of a metallic ion complex (adsorption of complexes, Eqn. 9-13b) is determining the rate, the Tafel constant, a-sp, will be obtained from Eqn. 9-18. In this discussion we have assumed Pi = Ps P then, Eqns. 9-19 and 9-20 follow ... 

For the purposes of this chapter, which focuses on comparisons of isocyanide binding in transition metal complexes and isocyanide adsorption on metal surfaces, we first summarize known modes of isocyanide binding to one, two and three metals in their complexes. In such complexes, detailed structural features of isocyanide attachment to the metals have been established by single-crystal X-ray diffraction studies. On the other hand, modes of isocyanide attachment to metal atoms on metal surfaces are proposed on the basis of comparisons of spectroscopic data for adsorbed isocyanides with comparable data for isocyanides in metal complexes with known modes of isocyanide attachment. 

Recent studies indicate that the adsorption of metal ions is controlled only in part by the concentration of the free (aquo) metal ion of considerable importance is the ability of hydroxo and other complex ions and molecules to adsorb. There have been two apparently divergent approaches to describe the role played by hydroxo metal complexes in adsorption at solid-aqueous electrolyte interfaces. Matijevic et al. (9) have proposed that specific hydrolysis products—e.g., Al8(OH)2o4+ in the A1(III)-H20 system, are responsible for extensive coagulation and charge reversal of hydrophobic colloids. It has also been demonstrated by Matijevic that the free (aquo) species of transition and other metal ions... 

In this chapter, recent results are discussed In which the adsorption of nitric oxide and its Interaction with co-adsorbed carbon monoxide, hydrogen, and Its own dissociation products on the hexagonally close-packed (001) surface of Ru have been characterized using EELS (13,14, 15). The data are interpreted In terms of a site-dependent model for adsorption of molecular NO at 150 K. Competition between co-adsorbed species can be observed directly, and this supports and clarifies the models of adsorption site geometries proposed for the individual adsorbates. Dissociation of one of the molecular states of NO occurs preferentially at temperatures above 150 K, with a coverage-dependent activation barrier. The data are discussed in terms of their relevance to heterogeneous catalytic reduction of NO, and in terms of their relationship to the metal-nitrosyl chemistry of metallic complexes. 

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