Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Activation of an α-Diimine Ni(II) Precatalyst with AlMe3and AliBu3 : Catalytic and NMR and EPR Spectroscopy Studies. / Soshnikov, Igor E.; Semikolenova, Nina V.; Bryliakov, Konstantin P. и др.
в: Organometallics, Том 39, № 16, 24.08.2020, стр. 3034-3040.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
}
TY - JOUR
T1 - Activation of an α-Diimine Ni(II) Precatalyst with AlMe3and AliBu3
T2 - Catalytic and NMR and EPR Spectroscopy Studies
AU - Soshnikov, Igor E.
AU - Semikolenova, Nina V.
AU - Bryliakov, Konstantin P.
AU - Antonov, Artem A.
AU - Sun, Wen Hua
AU - Talsi, Evgenii P.
N1 - Publisher Copyright: Copyright © 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/8/24
Y1 - 2020/8/24
N2 - The nature of Ni(II) and Ni(I) species formed upon the activation of the N,N-α-diimine Ni(II) precatalyst LNiIIBr2 (1) with AlMe3, MMAO, and AliBu3 has been studied by NMR and EPR spectroscopy (L = 1,4-bis(2,4,6-trimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene). It has been shown that the paramagnetic complex 3AlMe3 with the proposed structure [LNiI(μ-Me)2AlMe2] or [(L•-)NiII(μ-Me)2AlMe2] predominates in the reaction solution of 1/AlMe3 at Al/Ni > 10. Upon activation of 1 with MMAO (Al/Ni > 20-30), nickel predominantly exists in the form of the structurally similar complex 3MMAO ([LNiI(μ-Me)2AliBu2] or [(L•-)NiII(μ-Me)2AliBu2]). The reaction of 1 with AliBu3 leads to rapid ligand scrambling, affording the EPR-active complex 4 ([(L•-)AliBu2]). The latter process is accompanied by Ni reduction to the zerovalent state. Possible roles of the observed species in the catalytic systems are discussed.
AB - The nature of Ni(II) and Ni(I) species formed upon the activation of the N,N-α-diimine Ni(II) precatalyst LNiIIBr2 (1) with AlMe3, MMAO, and AliBu3 has been studied by NMR and EPR spectroscopy (L = 1,4-bis(2,4,6-trimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene). It has been shown that the paramagnetic complex 3AlMe3 with the proposed structure [LNiI(μ-Me)2AlMe2] or [(L•-)NiII(μ-Me)2AlMe2] predominates in the reaction solution of 1/AlMe3 at Al/Ni > 10. Upon activation of 1 with MMAO (Al/Ni > 20-30), nickel predominantly exists in the form of the structurally similar complex 3MMAO ([LNiI(μ-Me)2AliBu2] or [(L•-)NiII(μ-Me)2AliBu2]). The reaction of 1 with AliBu3 leads to rapid ligand scrambling, affording the EPR-active complex 4 ([(L•-)AliBu2]). The latter process is accompanied by Ni reduction to the zerovalent state. Possible roles of the observed species in the catalytic systems are discussed.
KW - ETHYLENE POLYMERIZATION BEHAVIOR
KW - NICKEL-COMPLEXES
KW - PALLADIUM
KW - COPOLYMERIZATION
UR - http://www.scopus.com/inward/record.url?scp=85089964084&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.0c00395
DO - 10.1021/acs.organomet.0c00395
M3 - Article
AN - SCOPUS:85089964084
VL - 39
SP - 3034
EP - 3040
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 16
ER -
ID: 25285659