How Close Is Too Close? Polymerization Behavior and Monomer-Dependent Reorganization of a Bimetallic Salphen Organotitanium Catalyst

Invergo, Anna M.; Liu, Shaofeng; Dicken, Rachel D.; Mouat, Aidan R.; Delferro, Massimiliano; Lohr, Tracy L.; Marks, Tobin J.

doi:10.1021/acs.organomet.8b00220

Title: How Close Is Too Close? Polymerization Behavior and Monomer-Dependent Reorganization of a Bimetallic Salphen Organotitanium Catalyst

Journal Article · Wed Jul 25 00:00:00 EDT 2018 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.8b00220· OSTI ID:1870994

Invergo, Anna M. ^[1]; Liu, Shaofeng ^[1]; Dicken, Rachel D. ^[1]; Mouat, Aidan R. ^[1];

^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)

The binuclear salphen Ti polymerization catalyst N,N'-1,2-phenylene[(salicylideneaminato)Ti(Cp*)Me₂)]₂ (2) is synthesized by reaction of salphen-H₂ with Cp*TiMe₃. Mononuclear [N-(2,6-diisopropyl)phenyl(salicylideneaminato)]Ti(Cp*)Me₂ (1) serves as a control. Activation studies of 2 with cocatalyst Ph₃C⁺B(C₆F₅)₄^– yield the cationic polymerization-inactive complex [N,N'-1,2-phenylene(salicylideneaminato)Ti(Cp*)]⁺B(C₆F₅)₄^– (4) and polymerization-active Cp*TiMe₂⁺B(C₆F₅)₄^–. Polymerization studies comparing 2 with Cp*TiMe₃ suggest that, within the catalytic time frame, while 2 retains bimetallic character under an ethylene atmosphere, it rapidly decomposes to 4 and Cp*TiMe₂⁺ in the presence of 1-hexene. These monomer-dependent reorganization results highlight the importance of olefin polymerization activation mechanistic studies while providing insight for improved bimetallic catalyst design.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: FG02-03ER15457; CHE-1464488; FG02-86ER13511

OSTI ID:: 1870994

Journal Information:: Organometallics, Vol. 37, Issue 15; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: How Close Is Too Close? Polymerization Behavior and Monomer-Dependent Reorganization of a Bimetallic Salphen Organotitanium Catalyst

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