Coordinated template catalysts

Other Reactions Catalyzed by Coordinated Template Catalysts... 

Scheme 6-20 Coordinated template catalyst 47 and cofactor analogues attached covalently to cyclodextrins in biomimetic catalysis.

Since the coordination almost certainly involves the transition metal atom, there is a resemblance here to anionic polymerization. The coordination is an important aspect of the present picture, since it is this feature which allows the catalyst to serve as a template for stereoregulation. 

The strategy used to design active and selective catalysts was based on the following five factors for regulation, (i) conformation of ligands coordinated to Rh atom (ii) orientation of a vacant site on Rh (iii) cavity with the template molecular shape for reaction space produced behind template removal (iv) architecture of the cavity wall and (v) micropore in inorganic polymer-matrix overlayers stabilizing the active species at the surface [46, 47, 71]. 

We started this templated approach to catalyst encapsulation using tris(mefa-pyridyl)phosphine and zinc(ii)TPP (TPP = tetraphenylporphyrin) [7]. From NMR and UV/Vis titration experiments we found a selective assembly process via coordination of the nitrogen to the zinc(ii)TPP, rendering the phosphine donor atom completely encapsulated by the three porphyrin components (Figure 8.4). The phosphine center is still available for coordination to transition metals, providing... 

Scheme 8.2 Formation of catalyst assemblies by selective pyri-dine-zinc(ii) coordinative motifs using zinc(ii)salphen complexes and different pyridylphosphine templates.

The rhodium(II) catalysts and the chelated copper catalysts are considered to coordinate only to the carbenoid, while copper triflate and tetrafluoioborate coordinate to both the carbenoid and alkene and thus enhance cyclopropanation reactions through a template effect.14 Palladium-based catalysts, such as palladium(II) acetate and bis(benzonitrile)palladium(II) chloride,l6e are also believed to be able to coordinate with the alkene. Some chiral complexes based on cobalt have also been developed,21 but these have not been extensively used. 

Apparently, the large optically active (— )-diop ligand (58) acts as a template during either the initial tr-coordination step or n—tr-rearrangement step in the mechanism proposed for hydrogenation via a homogeneous catalyst (69). 

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