Abiotic supramolecular catalysis

In addition to the mimicking of natural enzymes, a fascinating goal in supramolecular chemistry is the development of entirely artificial catalysts. While both heterogeneous and homogeneous catalysts based in particular on coordination of ligands to transition metals are common, supramolecular catalysts use either exclusively, or in addition, some aspect of molecular recognition and non-covalent 

Supramolecular catalysis may also involve the combination of a host cavity and a metal active site as in the bis(diphenylphosphino)calix[4]arene nickel(II) complex 12.40 which acts as an efficient catalyst for ethylene and propylene polymerisation, and in tandem with zirconocene dichloride, for the formation of linear low-density polyethylene. In the latter case the complex gives very little branching - a significant advantage. The key to the effectiveness of the catalyst involves calixarene-indnced changes in the bite angle at the Ni(II) centre, which is square planar in the active form of the catalyst. 

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The systems described in this chapter possess properties that define supramolecular reactivity and catalysis substrate recognition, reaction within the supermolecule, rate acceleration, inhibition by competitively bound species, structural and chiral selectivity, and catalytic turnover. Many other types of processes may be imagined. In particular, the transacylation reactions mentioned above operate on activated esters as substrates, but the hydrolysis of unactivated esters and especially of amides under biological conditions, presents a challenge [5.77] that chemistry has met in enzymes but not yet in abiotic supramolecular catalysts. However, metal complexes have been found to activate markedly amide hydrolysis [5.48, 5.58a]. Of great interest is the development of supramolecular catalysts performing synthetic... 

In this chapter we focus on supramolecular chemical reactivity. In particular this means predominantly the role supramolecular chemistry plays in accelerating or understanding chemical reactions. There are close parallels between artificial, abiotic supramolecular reactivity and biochemistry, for example in the study of enzymes, Nature s catalysts - described in Section 2.6. Synthetic catalysts can both model natural ones and allow the design of new, different kinds of reactions. Supramolecular catalysis sits somewhere between chemical catalysis (transition metal and organocatalysis) and biology. Some considerations within various kinds of catalysis are summed up in the chart shown in Figure 12.1. 

Abiotic supramolecular systems can be used as models for biological catalysis and as catalysts for other reactions that are not of biological origin. 

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