Understanding molecular kinetics should be the first step towards reaction control for any chemical process. In the specific case of catalytic olefin polymerization, in the sixty years after the initial discoveries very many tried, many claimed to have made it, a few admitted to have failed; the author of this talk belongs in the latter. On the other hand, like Itsy-Bitsy Spider he tried again and again, and ultimately achieved some success by integrating quenched-flow methods with DFT modeling. Several cases will be presented to illustrate how the same basic reaction can proceed according to diverse mechanisms ranging from trivial to fully counter-intuitive, depending on the steric and electronic features of the catalytic species. Based on the observed facts, tentative relationships between catalyst structure and properties will be proposed. Moreover, the concept of 'dormant' site will be re-visited with an eye to reaction time scale.

Molecular kinetics of catalytic olefin polymerization: Back to the start and then a bit forward

250th National Meeting (2015)

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