Journal
ACS CATALYSIS
Volume 6, Issue 11, Pages 7989-7993Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.6b02738
Keywords
catalysis; olefin polymerization; Ti-C homolysis; functionalized chain ends; DFT; Ti(IV)/Ti(III) oxidation state changes; 2,1-insertions
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Propene polymerization using Ti Cp-phosphinimide catalysts in toluene and related aromatic solvents leads to the formation of benzyl-terminated polymer chains. End-group analysis suggests that these are formed after a 2,1 insertion event; density functional theory (DFT) studies support a mechanism involving homolysis of a Ti-sec-alkyl bond. This reaction could enable the catalytic formation of chain-end functionalized polyolefins. More importantly, it demonstrates that Ti-C homolysis might limit activity but does not necessarily constitute an irreversible deactivation mechanism.
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