Solution

ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2024/paper-2/b8/b/iii/solution

Write for the current growing chain. Propene first binds at the available site of , giving a coordinated alkene adjacent to the metal-bound chain. In the Cossee-Arlman mechanism, the chain migrates to the substituted alkene carbon while the terminal carbon forms the new Zr–C bond:
The electron-pair arrows for insertion take the old Zr–R bond toward the substituted alkene carbon and the alkene pi bond toward the new Zr–terminal-carbon bond. A four-center arrangement permits both bonds to change in one migratory insertion; Zr remains Zr(IV). The product again has an accessible site, so coordination and insertion can repeat.
Predominant 1,2 insertion leaves a primary Zr–CH chain end and generates head-to-tail polypropylene. It avoids the more crowded alternative secondary Zr–CH(Me) end and unfavorable methyl contacts with the cyclopentadienyl ligands in the insertion geometry. This explains regioselectivity. An unbridged, unsubstituted zirconocene does not by itself establish a fixed tacticity; the schematic alignment of methyl groups in a polymer drawing is not evidence for an isotactic product.

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