Complexes with active centres

There exist compounds the molecules of which exhibit the character of donor-acceptor complexes with separated centres of positive and negative charge. Initiator and monomer sometimes do not produce a classical ion pair, but a molecule carrying both types of opposite charge. In such a case, the generated zwitterions (amphiions) represent a special class of active centres. 

When donor—acceptor complexes are formed from the monomers, they can take part in copolymerization. When the equilibrium constants of complex formation are not extremely high, both complexes and monomers coexist and compete with active centres in the reaction. In addition, the reverse case may occur when one part of the active centres forms complexes with some component of the medium, the reactivity of the complexed centers is, of course, different from that of the free centres. The situation is formally similar to that of the preceding paragraph. 

The active centres, from where the Polymer chain growth propagates, are formed at the surface of the solid phase of the catalyst complex, and the monomer is complexed with the metal ion of the active centre before its insertion into the growing chain. 

This complex then acts as the active centre. The monomer is then attracted towards the Ti-C bond (C from the alkyl group R) in active centre, when it formes a p complex with the Ti ion as under ... 

Studies in the area of electrochemical molecular recognition deal with bifunctional receptor molecules that contain not only binding sites but also one or more redox-active centres whose electron transfer reaction is coupled to the receptor s complexation. Such systems can be described by the scheme of squares as shown in Scheme 1. 

The effect of a biologically active compound is based on its ability to form a complex with a receptor. The intensity of the biological effect is proportional to the stability of this complex, which is dependent on the strength of the interaction of the effector molecule with the active centre of the receptor. The electron structure of the molecule can be decisive for this interaction and this may explain the correlation of ionization potentials and pharmacological properties of certain compounds. 

Preliminary results on the kinetics of the polymerization and the efficiency of initiation of the isotactic polymerizations initiated by t-BuMgBr in toluene solution are consistent with the Bateup mechanism proposed for the stereoblock and syndio-tactic-like polymerizations initiated by n-BuMgBr in THF-rich solution — a mechanism which involves initiation and propagation through monomer — active centre complexes (5,8). 

If the proposed structure was true, then a solvent of higher solvating power, such as dme, should decrease the stability of the intramolecular complex. Using sodium as the counterion part of the active centres should exist in the form of externally solvated contact ion pairs or even solvent-separated ion pairs. With caesium as the counterion there should be little change, because this cation is only poorly solvated by both solvents and consequently the possibility of solvent-separated ion pairs to be found should be extremely small. 

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