Metal complexes, adsorption phases

Surface science results have thrown new light on modified (chiral) metal surfaces, highlighting new phenomena such as complex adsorption phases, two-dimensional organization and the creation of extended chiral surfaces [307]. New strategies to immobilize an asymmetric catalyst onto a support (adsorption, encapsulation, tethering using a covalent bond and electrostatic interaction) also result in an... 

Supported metal carbonyl clusters are alternatively formed from mononuclear metal complexes by surface-mediated synthesis [5,13] examples are [HIr4(CO)ii] formed from Ir(CO)2(acac) on MgO and Rh CCOlie formed from Rh(CO)2(acac) on y-Al203 [5,12,13]. These syntheses are carried out in the presence of gas-phase CO and in the absence of solvents. Synthesis of metal carbonyl clusters on oxide supports apparently often involves hydroxyl groups or water on the support surface analogous chemistry occurs in solution [ 14]. A synthesis from a mononuclear metal complex precursor is usually characterized by a yield less than that attained as a result of simple adsorption of a preformed metal cluster, and consequently the latter precursors are preferred when the goal is a high yield of the cluster on the support an exception is made when the clusters do not fit into the pores of the support (e.g., a zeolite), and a smaller precursor is needed. 

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 Ziegler-type catalysts contain also a metal-alkyl, like triethylaluminum. They work usually at moderate temperature and pressure. The most active catalysts for polymer hydrogenation are the noble metal complex catalysts, and they can also be used for reduction of elastomers in the latex phase. The most difficult task is the removal of the catalyst from the reaction mixture. The methods used are based on extraction, adsorption, absorption or on their combination. 

Another unique and specific feature of the interfacial reaction is the formation of aggregate of dye molecules, metal complexes, and other solvophobic molecules. As reported in many interfacial adsorption systems, the saturated interfacial concentration of usual molecules is of the order of 10 10mol/cm2, which can be attained even under an extremely low bulk phase concentration. This means that the liquid-liquid interface is ready to be saturated to form a two-dimensionally condensed state for the adsorbate. In solvent extraction process of metal ions, we used to find formation of some precipitate at the interface, which is called crud. The study of the interfacial aggregate is therefore important to know the real interfacial reaction as met in the industrial solvent extraction where rather concentrated solutes have to be treated. 

What is the specific feature in the reaction at the liquid/liquid interface The catalytic role of the interface is of primary importance in solvent extraction and other two-phase reaction kinetics. In solvent extraction kinetics, the adsorption of the extractant or an intermediate complex at the liquid/liquid interface significantly increased the extraction rate. Secondly, interfacial accumulation or concentration of adsorbed molecules, which very often results in interfacial aggregation, is an important role played by the interface. This is because the interface is available to be saturated by an extractant or mehd complex, even if the concentration of the extractant or metal complex in the bulk phase is very low. Molecular recognition or separation by the interfacial aggregation is the third specific feature of the interfacial reaction and is thought to be closely related to the biological functions of cell membranes. In addition, molecular diffusion of solute and solvent molecules at the liquid/liquid interface has to be elucidated in order to understand the molecular mobility at the interface. In this chapter, some examples of specific... 

Adsorption of a high-boiling solvent onto a high-surface-area microporous solid yields a supported liquid phase that can be removed from the sohd only by extraction with a second solvent or by distillation at high temperature under vacuum. Under typical reaction conditions, a solid that contains a supported liquid phase looks and behaves as a solid, yet it can dissolve small quantities of a metal complex into the supported phase. One of the first examples of this arrangement was achieved with the immobilization of Rh(CO)(PPh3)2Cl in benzyl butyl phthalate on silica. The supported complex was successfiilly used to effect the gas-phase hydroformylation of propene. 

Sorption of Cu(tfac)2 on a column depends on the amount of the compound injected, the content of the liquid phase in the bed, the nature of the support and temperature. Substantial sorption of Cu(tfac)2 by glass tubing and glass-wool plugs was observed. It was also shown that sorption of the copper chelate by the bed is partialy reversible . The retention data for Cr(dik)3, Co(dik)3 and Al(dik)3 complexes were measured at various temperatures and various flow rates. The results enable one to select conditions for the GC separation of Cr, Al and Co S-diketonates. Retention of tfac and hfac of various metals on various supports were also studied and were widely used for the determination of the metals. Both adsorption and partition coefficients were found to be functions of the average thickness of the film of the stationary phase . Specific retention volumes, adsorption isotherms, molar heats and entropy of solution were determined from the GC data . The retention of metal chelates on various stationary phases is mainly due to adsorption at the gas-liquid interface. However, the classical equation which describes the retention when mixed mechanisms occur is inappropriate to represent the behavior of such systems. This failure occurs because both adsorption and partition coefficients are functions of the average thickness of the film of the stationary phase. It was pointed out that the main problem is lack of stability under GC conditions. Dissociation of the chelates results in a smaller peak and a build-up of reactive metal ions. An improvement of the method could be achieved by addition of tfaH to the carrier gas of the GC equipped with aTCD" orFID" . ... 

Propene.—Dent and Kokes demonstrated most elegantly, using i.r. spectroscopy and 6 selectively labelled propenes, that on adsorption propene forms both a ff-complex (vc=c shifted 30 cm from the value in gas phase) and a TT-allyl species ( CH2—CH—CH2, i c = c shifted 100 cm" ). The latter had a saturation coverage of 30% and was analogous to the 7r-allyl ligands of transition metal complexes. They showed that it displaced type (/) hydrogen to C3H5 H... 

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