2,4,6-Triphenylpyridinium-Substituted Neutral Nickel Catalysts: Ethylene Polymerization, Influence of Activator, Catalyst Decomposition, and End-Group Analysis

Janeta, Mateusz; Carmona, Alberto Feliciano; Wang, Xiqu; Brookhart, Maurice; Daugulis, Olafs

doi:10.1021/acs.organomet.4c00512

2,4,6-Triphenylpyridinium-Substituted Neutral Nickel Catalysts: Ethylene Polymerization, Influence of Activator, Catalyst Decomposition, and End-Group Analysis

Journal Article · Thu Feb 27 00:00:00 EST 2025 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.4c00512· OSTI ID:2530205

^[1]; Carmona, Alberto Feliciano ^[2]; Wang, Xiqu ^[2]; Brookhart, Maurice ^[2]; ^[2]

University of Houston, TX (United States); University of Wrocław (Poland); University of Houston
University of Houston, TX (United States)

The reactivity of 2,4,6-triphenylpyridinium-substituted nickel(II)-salicyliminato catalysts in ethylene polymerization has been explored. Here, the known complex 6a equipped with a 2,6-diisopropylphenyl group affords polyethylene with M_n = 10-12 kDa at 19 ⁰C, while 8a possessing the bulkier 2,6-diphenylphenyl moiety gives polymer with M_n = 270-310 kDa. The stability of catalyst 6a depends on the borane activator. If B(C₆F₅)₃ is employed, enhanced stability is observed compared with using 3H₂O·B(C₆F₅)₃ activator. Catalyst 6a decomposes forming a hydroxyl-bridged dimer 14 which may be reac-tivated, albeit inefficiently, by excess borane activator. Polymer formed by 6a contains ca. 3-6% of 2-trifluoromethylphenyl, pentafluorophenyl, and 3,5-bis(trifluoromethyl)phenyl end groups combined. The pentafluoro-phenyl end group originates from reaction of 6a with borane activator, and from reactivation of hydroxyl-bridged dimer 14. 3,5-Bis(trifluoromethyl)phenyl end groups are likely formed in a reaction sequence initiated by protonation of one aryl group in NaBArF which creates B[C₆H₃(CF₃)₂]₃. The triarylborane can then react with 6a or 14 transferring the 3,5-bis(trifluoromethyl)phenyl group to nickel.

View Accepted Manuscript (DOE)

Research Organization:: University of Houston, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation

Grant/Contract Number:: SC0024250

OSTI ID:: 2530205

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 5 Vol. 44; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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