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Formation of Ni(I) Species upon Activation of 5,6,7-Trihydroquinolin-8-imine Nickel(II) Dihalides with MAO and MMAO Full article

Journal Organometallics
ISSN: 1520-6041 , E-ISSN: 0276-7333
Output data Year: 2024, Volume: 43, Number: 24, Pages: 3204–3215 Pages count : DOI: 10.1021/acs.organomet.4c00227
Authors Stepanov Artem D. 1,2 , Soshnikov Igor E. 1,2 , Semikolenova Nina V. 1 , Bryliakov Konstantin P. 3 , Talsi Evgenii P. 1,2
Affiliations
1 Boreskov Institute of Catalysis, Novosibirsk 630090, Russia
2 Novosibirsk State University, Novosibirsk 630090, Russia
3 Zelinskii Institute of Organic Chemistry, Moscow 119991, Russia

Abstract: Reactions between (E)-N-(2,6-diisopropylphenyl)-2-methyl-6,7-dihydroquinolin-8(5H)-imine nickel(II) dihalides and organoaluminum compounds AlMe3, AliBu3, MAO, and MMAO were monitored using EPR spectroscopy in situ. It was found that rapid one-electron reduction of the Ni(II) center results in formation of a variety of monovalent nickel species which are stable at room temperature in an oxygen-free atmosphere. On the basis of the EPR data obtained, these compounds were assigned to the heterobinuclear nickel-aluminum complexes of the type LNiI(μ-R)2AlX2, where L = N,N′-donor ligand, R = Me, iBu, H, Br, or Cl bridge, and X = Me, iBu, Br or, Cl, depending on conditions. Formation of the dihydride-bridged LNiI(μ-H)2AlX2 complex was confirmed using deuterium-labeled compounds. In the presence of an excess of ethylene or 1-hexene, LNiI(μ-R)2AlX2 eliminates RAlX2 to afford LNiIR(C2H4) or LNiIR(C6H12) species, respectively. Structural assignments of the NiI species are supported by DFT calculations of their g-tensor values.
Cite: Stepanov A.D. , Soshnikov I.E. , Semikolenova N.V. , Bryliakov K.P. , Talsi E.P.
Formation of Ni(I) Species upon Activation of 5,6,7-Trihydroquinolin-8-imine Nickel(II) Dihalides with MAO and MMAO
Organometallics. 2024. V.43. N24. P.3204–3215. DOI: 10.1021/acs.organomet.4c00227 WOS Scopus OpenAlex
Identifiers:
Web of science: WOS:001333423900001
Scopus: 2-s2.0-85206643602
OpenAlex: W4403418566
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