Reaction of ether and thioether functionalised 1-Alkenes with the cationic permethylzirconocene olefin polymerisation catalyst [(η5-C5Me5)2ZrMe]+. Molecular structure of the insertion product [(η5-C5Me5)2ZrCH2CH(Me)CH2OEt]+1

Add time:07/22/2019    Source:sciencedirect.com

Reaction of [(η5-C5Me5)2ZrMe][MeB(C6F5)3] (1) with (thio)ether functionalised alkenes: 3-ethoxy-1-propene and 3-(methylthio)-1-propene gives stable insertion products [(η5-C5Me5)2ZrCH2CH(Me)CH2XR][MeB(C6F5)3] (2: X=O, R=Et; 3: X=S, R=Me) in which the (thio)ether function is intramolecularly coordinated to zirconium. The molecular structure of 2 shows a regular 1-oxa-2-zirconacyclopentane in an envelope conformation. The metallacycles in 2 and 3 are stable toward further insertion of (functionalised) alkenes and cannot be activated for ethene polymerisation by pre-complexation of the (thio)ether function with strong Lewis acids (AlCl3, MgCl2, B(C6F5)3 or [Ph3C]+). The strong alkylating co-catalyst Me3Al regenerates complex 1 by exchange of the (thio)ether function for methyl and thus initiates polymerisation of ethene.

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