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

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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. / Stepanov, Artem D.; Soshnikov, Igor E.; Semikolenova, Nina V. et al.

In: Organometallics, 21.10.2024.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{a7abdbd3d01645b4962f9d1a15e0e806,

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

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.",

author = "Stepanov, {Artem D.} and Soshnikov, {Igor E.} and Semikolenova, {Nina V.} and Bryliakov, {Konstantin P.} and Talsi, {Evgenii P.}",

note = "This work was supported by the Russian Science Foundation, grant 24-23-00033. The access to the equipment of the Center of Collective Use {"}National Center of Catalysis Research{"} is acknowledged.",

year = "2024",

month = oct,

day = "21",

doi = "10.1021/acs.organomet.4c00227",

language = "English",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

}

RIS

TY - JOUR

T1 - Formation of Ni(I) Species upon Activation of 5,6,7-Trihydroquinolin-8-imine Nickel(II) Dihalides with MAO and MMAO

AU - Stepanov, Artem D.

AU - Soshnikov, Igor E.

AU - Semikolenova, Nina V.

AU - Bryliakov, Konstantin P.

AU - Talsi, Evgenii P.

N1 - This work was supported by the Russian Science Foundation, grant 24-23-00033. The access to the equipment of the Center of Collective Use "National Center of Catalysis Research" is acknowledged.

PY - 2024/10/21

Y1 - 2024/10/21

N2 - 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.

AB - 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.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85206643602&origin=inward&txGid=b6071f47b1a6316aebe7edb597cffff4

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001333423900001

UR - https://www.mendeley.com/catalogue/5c696ee1-bf72-3f36-ba7c-8e3d445c881b/

U2 - 10.1021/acs.organomet.4c00227

DO - 10.1021/acs.organomet.4c00227

M3 - Article

JO - Organometallics

JF - Organometallics

SN - 0276-7333

ER -

ID: 61165601