TY - JOUR
T1 - Synthesis of Cationic, Dimeric α-Diimine Nickel Hydride Complexes and Relevance to the Polymerization of Olefins
AU - Léonard, Nadia G.
AU - Yruegas, Sam
AU - Ho, Suzzy C.
AU - Sattler, Aaron
AU - Bezdek, Máté J.
AU - Chirik, Paul J.
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/7/27
Y1 - 2020/7/27
N2 - Well-defined nickel hydride complexes bearing aryl-substituted α-diimine (iPrDI = N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediimine or MesDI = N,N′-bis(2,4,6-trimethylphenyl)-2,3-butanediimine) ligands have been synthesized and studied for the oligomerization of linear internal olefins. Neutral diimine nickel hydride dimers, [(iPrDI)Ni(μ2-H)]2 (1) and [(MesDI)Ni(μ2-H)]2 (2), were explored as synthetic entries to monomeric cationic hydride complexes; however, the dimeric structure was preserved upon oxidation with ferrocenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([Cp2Fe][BArF24]). The monocationic nickel hydride dimers, [(iPrDI)Ni(μ2-H)]2[BArF24] (3) and [(MesDI)Ni(μ2-H)]2[BArF24] (4), were characterized by X-ray diffraction, electron paramagnetic resonance, and nuclear magnetic resonance spectroscopies that support a mixed-valent nickel(I)-nickel(II) assignment. The catalytic activity of 3 and 4 for the oligomerization of 1-hexene, trans-2-hexene, and trans-3-hexene was determined and showed decreased activity as compared to the corresponding nickel dibromide precatalyst activated by methylaluminoxane.
AB - Well-defined nickel hydride complexes bearing aryl-substituted α-diimine (iPrDI = N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediimine or MesDI = N,N′-bis(2,4,6-trimethylphenyl)-2,3-butanediimine) ligands have been synthesized and studied for the oligomerization of linear internal olefins. Neutral diimine nickel hydride dimers, [(iPrDI)Ni(μ2-H)]2 (1) and [(MesDI)Ni(μ2-H)]2 (2), were explored as synthetic entries to monomeric cationic hydride complexes; however, the dimeric structure was preserved upon oxidation with ferrocenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([Cp2Fe][BArF24]). The monocationic nickel hydride dimers, [(iPrDI)Ni(μ2-H)]2[BArF24] (3) and [(MesDI)Ni(μ2-H)]2[BArF24] (4), were characterized by X-ray diffraction, electron paramagnetic resonance, and nuclear magnetic resonance spectroscopies that support a mixed-valent nickel(I)-nickel(II) assignment. The catalytic activity of 3 and 4 for the oligomerization of 1-hexene, trans-2-hexene, and trans-3-hexene was determined and showed decreased activity as compared to the corresponding nickel dibromide precatalyst activated by methylaluminoxane.
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U2 - 10.1021/acs.organomet.0c00257
DO - 10.1021/acs.organomet.0c00257
M3 - Article
AN - SCOPUS:85088375577
SN - 0276-7333
VL - 39
SP - 2630
EP - 2635
JO - Organometallics
JF - Organometallics
IS - 14
ER -