Activation of an α-Diimine Ni(II) Precatalyst with AlMe3 and AliBu3: Catalytic and NMR and EPR Spectroscopy Studies | Sciact - CRIS-system of Boreskov Institute of Catalysis

Activation of an α-Diimine Ni(II) Precatalyst with AlMe3 and AliBu3: Catalytic and NMR and EPR Spectroscopy Studies Full article

Journal

Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041

Output data

Year: 2020, Volume: 39, Number: 16, Pages: 3034-3040 Pages count : 7 DOI: 10.1021/acs.organomet.0c00395

Tags

ETHYLENE POLYMERIZATION BEHAVIOR; NICKEL-COMPLEXES; PALLADIUM; COPOLYMERIZATION

Authors

Soshnikov Igor E. ^1,2 , Semikolenova Nina V. ¹ , Bryliakov Konstantin P. ^1,2 , Antonov Artem A. ^1,2 , Sun Wen-Hua ³ , Talsi Evgenii P. ^1,2

Affiliations

1	Boreskov Institute of Catalysis, Pr. Lavrentieva, 5, 630090 Novosibirsk, Russian Federation
2	Novosibirsk State University Pirogova 1, 630090 Novosibirsk, Russian Federation
3	State Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China

Funding (3)

1	Russian Foundation for Basic Research National Natural Science Foundation of China	18-53-80031 / 51861145303
2	Federal Agency for Scientific Organizations	0303-2016-0009
3	Chinese Academy of Sciences	2020VMA0028

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.

Soshnikov I.E. , Semikolenova N.V. , Bryliakov K.P. , Antonov A.A. , Sun W-H. , Talsi E.P.
Activation of an α-Diimine Ni(II) Precatalyst with AlMe3 and AliBu3: Catalytic and NMR and EPR Spectroscopy Studies
Organometallics. 2020. V.39. N16. P.3034-3040. DOI: 10.1021/acs.organomet.0c00395 WOS Scopus РИНЦ AN OpenAlex

Submitted:	Jun 10, 2020
Published online:	Aug 10, 2020
Published print:	Aug 24, 2020

Web of science:	WOS:000563782500015
Scopus:	2-s2.0-85089964084
Elibrary:	45356930
Chemical Abstracts:	2020:1543605
OpenAlex:	W3048815163

DB	Citing
Scopus	17
Web of science	15
Elibrary	13
OpenAlex	17