Ship-in-a-bottle method

Scheme 15. Schematic description of chiral Co(salen) 45 synthesized in the cages of phenyl-modified SBA-16 through the ship in a bottle method.

When entrapment methods are being used for heterogenization, the size of the metal complex is more important than the specific adsorptive interaction. There are two different preparation strategies. The first is based on building up catalysts in well-defined cages of porous supports. This approach is also called the ship in a bottle method [29]. The other approach is to build up a polymer network around a preformed catalyst. 

VII. Formation of Metal Clusters by the Ship-in-a-Bottle Method... 

In some cases, the supported mononuclear metal complexes are precursors of catalysts formed during reaction. For example, MCM-41-supported [(=SiO)2Ta(=NH)(NH2)] and [(=SiO)2Ta(=NH)(NH2)(NH3)] [19] are formed by the reaction of [(=SiO)2TaH], [(=SiO)2TaH3], and NH3 (Fig. 19.2). These and other synthetic surface reactions such as the ship-in-a-bottle method are reviewed elsewhere [20, 21]. 

Up until the late seventies attempts to develop redox molecular sieves were mainly limited to the ion-exchange approach (see later). This situation changed dramatically with the discovery, by Enichem scientists in 1983 [6,7], of the unique activity of titanium silicalite-1 (TS-1) as a catalyst for oxidations with 30% aqueous hydrogen peroxide. Following the success of TS-1, interest in the development, and application in organic synthesis, of redox molecular sieves has increased exponentially and has been the subject of several recent reviews [8-11]. It has even provoked a revival of interest in another approach to producing redox molecular sieves the so-called ship-in-a-bottle method [12-15]. 

Phthalocyanine complexes within zeolites have also been prepared by the ship-in-a-bottle method (see Section 6.6), and have subsequently been investigated as selective oxidation catalysts, where their planar metal-N4 centres mimic the active sites of enzymes such as cytochrome P450, which is able to oxidize alkanes with molecular oxygen. Cobalt, iron and ruthenium phthalocyanines encapsulated within faujasitic zeolites are active for the oxidation of alkanes with oxygen sources such as iodosobenzene and hydroperoxides. Following a similar route, Balkus prepared Ru(II)-perchloro- and perfluorophthalocyanines inside zeolite X and used these composites for the selective catalytic oxidation of alkanes (tert-butylhydroperoxide). The introduction of fluorinated in place of non-fluorinated ligands increases the resistance of the complex to deactivation. 

Another way of immobilizing catalyst complexes might be to trap them in the pores of solid particles, for instance by synthesizing the complex inside the pores of a zeolite ( ship in a bottle ). Another method could be to trap catalyst complexes in porous materials and deposit a membrane at the outer. surface. These methods of immobilizing a homogeneous catalyst do not involve chemical linkage between the catalyst and the carrier. The fixation is the result of steric hindrance. 

Common to all encapsulation methods is the provision for the passage of reagents and products through or past the walls of the compartment. In zeolites and mesoporous materials, this is enabled by their open porous structure. It is not surprising, then, that porous silica has been used as a material for encapsulation processes, which has already been seen in LbL methods [43], Moreover, ship-in-a-bottle approaches have been well documented, whereby the encapsulation of individual molecules, molecular clusters, and small metal particles is achieved within zeolites [67]. There is a wealth of literature on the immobilization of catalysts on silica or other inorganic materials [68-72], but this is beyond the scope of this chapter. However, these methods potentially provide another method to avoid a situation where one catalyst interferes with another, or to allow the use of a catalyst in a system limited by the reaction conditions. For example, the increased stability of a catalyst may allow a reaction to run at a desired higher temperature, or allow for the use of an otherwise insoluble catalyst [73]. 

Immobilization method Covalent binding Adsorption Ion pair formation Entrapment or ship-in-a-bottle ... 

The second example demonstrated immobilization via ship in a bottle , ionic, metal center, and covalent bonding approaches of the metal-salen complexes. Zeolites X and Y were highly dealuminated by a succession of different dealumi-nation methods, generating mesopores completely surrounded by micropores. This method made it possible to form cavities suitable to accommodate bulky metal complexes. The catalytic activity of transition metal complexes entrapped in these new materials (e.g, Mn-S, V-S, Co-S, Co-Sl) was investigated in stereoselective epoxidation of (-)-a-pinene using 02/pivalic aldehyde as the oxidant. The results obtained with the entrapped organometallic complex were comparable with those of the homogeneous complex. 

Metal complexes have been immobilised in many different ways, e.g. covalent anchoring (by grafting or tethering) to inorganic supports, immobilisation by occlusion in zeolitic micro- or mesopores (ship-in-a-bottle concept), or as supported liquid-phase catalysts [2], In recent reviews the potential of (chiral) metal complexes immobilised by these different methods has been evaluated [3,4,5]. 

The ship-in-a-bottle technique is perhaps the most common method for encapsulation of transition metal complexes. In this way the tetradentate Schiff base ligand SALEN (bis-salicylidene) ethylenediamine can diffuse through the 12 MR windows of faujasite. Then, when complexed with a previously exchanged metal ion, nearly square planar coordination geometry is formed inside the a-cages [97-100], Mn complexes with a chiral ligand, prepared by the ship-in-a-bottle technique inside Y and EMT zeolites, have enantioselectively carried at the epoxidation of olefins [101,102]. 

Nuetral templates may not be bound to the zeolite surface but simply trapped. This is the basis of our zeolite synthesis method for the preparation of ship-in-a-bottle metal complexes, ie crystallization of the zeolite around a metal chelate complex. Zeolite encapsulated metal complexes have many applications, ranging from shape selective catalysis [9] to magnetic resonance imaging contrast agents [10]. 

Figure 3. Pictorial illustration of ship-in-a-bottle synthesis of metal clusters, Rh6(CO)i6 assembled in NaY cages by the suecessive carbonylation of Rh ions using CO + H2O or CO + H2 as building blocks, which are introduced by the ion-exchange methods and gas admission.

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