Catalysis in Interphases

The term chemistry in interphases was first introduced in the field of reverse-phase chromatography [41], In 1995 Lindner et al. transferred the concept to the area of transition metal catalysis [42] and in a recent review the concept is explained in detail [43], The interphase is defined as a region within a system in which the stationary and a mobile component penetrate on a molecular level without the formation of a homogeneous mixture. In these regions the reactive centre on the stationary phase 

Lindner et al. carried out detailed studies on the use of the sol-gel procedure to obtain new materials as suitable matrices [45]. A co-condensation of Si(OR)4, Si(OR)3-spacer-Si(OR)3 and Si(OR)3-spacer-ligand resulted in new hybrid materials, the properties of which strongly depended upon the spacer and the ratio of the different components used. Most of these materials were characterised with IR, EXAFS, and EDX spectroscopy, scanning electron microscopy and solid state NMR spectroscopy. Solid state 31P NMR was used to quantify the mobility of the interphases the changes in line- 

4 used hemi-labile ligands such as 4, and their 

The use of dendrimers as supports to anchor transition metal catalysts has attracted considerable attention over the past decades [48] (see also Chapter 4 of this book). Several groups studied the use of dendrimers immobilised on insoluble supports [49], and this type of material meet the requirements for catalysis in interphases. Alper reported the use of diphosphine functionalised polyamidoamine (PAMAM) dendrimers 

Arya et al. used solid phase synthesis to prepare immobilised dendritic catalysts with the rhodium centre in a shielded environment to mimic nature s approach of protecting active sites in a macromolecular environment (e.g. catalytic sites inside enzymes) [51], Two generations PS immobilised rhodium-complexed dendrimers, 6 and the more shielded 7, were synthesised.The PS resin immobilised rhodium-complexed dendrimers were used in the hydroformylation of styrene, p-methoxystyrene, vinyl acetate and vinyl benzoate using a total pressure of 70 bar 1 1 CO/H2 at 45 °C in CH2C12. 

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The lesson learned from the catalysis in interphase approach is that the spacer between the insoluble support and the actual catalyst should be sufficiently long and soluble in the solvent of interest to obtain active catalysts. The use of supercritical fluids can also be very beneficial for the activity. Upon using Xantphos immobilised on silica in scC02 for example, the rates are only half of those of the homogeneous catalyst. Expressed as space-time yields the solid catalysts are almost an order of... 

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