Activation of Ethylene by N-Heterocyclic Carbene Coordinated Magnesium(I) Compounds

K. Yuvaraj; Iskander Douair; Laurent Maron; Cameron Jones

doi:10.1002/chem.202002380

Activation of Ethylene by N-Heterocyclic Carbene Coordinated Magnesium(I) Compounds

K. Yuvaraj, Iskander Douair, Laurent Maron, Cameron Jones

School of Chemistry

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

19 Citations (Scopus)

Abstract

Reactions of a series of magnesium(I) compounds with ethylene, in the presence of an N-heterocyclic carbene (NHC), have been explored. Treating [{(^MesNacnac)Mg}₂] (^MesNacnac=[HC(MeCNMes)₂]⁻, Mes=mesityl) with an excess of ethylene in the presence of two equivalents of :C{(MeNCMe)₂} (TMC) leads to the formal reductive coupling of ethylene, and formation of the 1,2-dimagnesiobutane complex, [{(^MesNacnac)(TMC)Mg}₂(μ-C₄H₈)]. In contrast, when the reaction is repeated in the presence of three equivalents of TMC, a mixture of the β-diketiminato magnesium ethyl, [(^MesNacnac)(TMC)MgEt], and the NHC coordinated magnesium diamide, [(^MesNacnac^-H)Mg(TMC)₂], results. Four related products, [(^ArNacnac)(TMC)MgEt] (Ar=2,6-dimethylphenyl (Xyl) or 2,6-diisopropylphenyl (Dip)) and [(^ArNacnac^-H)Mg(TMC)₂] (Ar=Xyl or Dip), were similarly synthesised and crystallographically characterized. Computational studies have been employed to investigate the mechanisms of the two observed reaction types, which appear dependent on the substitution pattern of the magnesium(I) compound, and the stoichiometric equivalents of TMC used in the reactions.

Original language	English
Pages (from-to)	14665-14670
Number of pages	6
Journal	Chemistry - A European Journal
Volume	26
Issue number	64
DOIs	https://doi.org/10.1002/chem.202002380
Publication status	Published - 17 Nov 2020

Keywords

ethylene
low oxidation state
magnesium(I)
reductive coupling

Access to Document

10.1002/chem.202002380

Cite this

@article{23e44671c8a04822823d1302334344fb,

title = "Activation of Ethylene by N-Heterocyclic Carbene Coordinated Magnesium(I) Compounds",

abstract = "Reactions of a series of magnesium(I) compounds with ethylene, in the presence of an N-heterocyclic carbene (NHC), have been explored. Treating [{(MesNacnac)Mg}2] (MesNacnac=[HC(MeCNMes)2]−, Mes=mesityl) with an excess of ethylene in the presence of two equivalents of :C{(MeNCMe)2} (TMC) leads to the formal reductive coupling of ethylene, and formation of the 1,2-dimagnesiobutane complex, [{(MesNacnac)(TMC)Mg}2(μ-C4H8)]. In contrast, when the reaction is repeated in the presence of three equivalents of TMC, a mixture of the β-diketiminato magnesium ethyl, [(MesNacnac)(TMC)MgEt], and the NHC coordinated magnesium diamide, [(MesNacnac-H)Mg(TMC)2], results. Four related products, [(ArNacnac)(TMC)MgEt] (Ar=2,6-dimethylphenyl (Xyl) or 2,6-diisopropylphenyl (Dip)) and [(ArNacnac-H)Mg(TMC)2] (Ar=Xyl or Dip), were similarly synthesised and crystallographically characterized. Computational studies have been employed to investigate the mechanisms of the two observed reaction types, which appear dependent on the substitution pattern of the magnesium(I) compound, and the stoichiometric equivalents of TMC used in the reactions.",

keywords = "ethylene, low oxidation state, magnesium(I), reductive coupling",

author = "K. Yuvaraj and Iskander Douair and Laurent Maron and Cameron Jones",

year = "2020",

month = nov,

day = "17",

doi = "10.1002/chem.202002380",

language = "English",

volume = "26",

pages = "14665--14670",

journal = "Chemistry - A European Journal",

issn = "1521-3765",

publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",

number = "64",

}

TY - JOUR

T1 - Activation of Ethylene by N-Heterocyclic Carbene Coordinated Magnesium(I) Compounds

AU - Yuvaraj, K.

AU - Douair, Iskander

AU - Maron, Laurent

AU - Jones, Cameron

PY - 2020/11/17

Y1 - 2020/11/17

N2 - Reactions of a series of magnesium(I) compounds with ethylene, in the presence of an N-heterocyclic carbene (NHC), have been explored. Treating [{(MesNacnac)Mg}2] (MesNacnac=[HC(MeCNMes)2]−, Mes=mesityl) with an excess of ethylene in the presence of two equivalents of :C{(MeNCMe)2} (TMC) leads to the formal reductive coupling of ethylene, and formation of the 1,2-dimagnesiobutane complex, [{(MesNacnac)(TMC)Mg}2(μ-C4H8)]. In contrast, when the reaction is repeated in the presence of three equivalents of TMC, a mixture of the β-diketiminato magnesium ethyl, [(MesNacnac)(TMC)MgEt], and the NHC coordinated magnesium diamide, [(MesNacnac-H)Mg(TMC)2], results. Four related products, [(ArNacnac)(TMC)MgEt] (Ar=2,6-dimethylphenyl (Xyl) or 2,6-diisopropylphenyl (Dip)) and [(ArNacnac-H)Mg(TMC)2] (Ar=Xyl or Dip), were similarly synthesised and crystallographically characterized. Computational studies have been employed to investigate the mechanisms of the two observed reaction types, which appear dependent on the substitution pattern of the magnesium(I) compound, and the stoichiometric equivalents of TMC used in the reactions.

AB - Reactions of a series of magnesium(I) compounds with ethylene, in the presence of an N-heterocyclic carbene (NHC), have been explored. Treating [{(MesNacnac)Mg}2] (MesNacnac=[HC(MeCNMes)2]−, Mes=mesityl) with an excess of ethylene in the presence of two equivalents of :C{(MeNCMe)2} (TMC) leads to the formal reductive coupling of ethylene, and formation of the 1,2-dimagnesiobutane complex, [{(MesNacnac)(TMC)Mg}2(μ-C4H8)]. In contrast, when the reaction is repeated in the presence of three equivalents of TMC, a mixture of the β-diketiminato magnesium ethyl, [(MesNacnac)(TMC)MgEt], and the NHC coordinated magnesium diamide, [(MesNacnac-H)Mg(TMC)2], results. Four related products, [(ArNacnac)(TMC)MgEt] (Ar=2,6-dimethylphenyl (Xyl) or 2,6-diisopropylphenyl (Dip)) and [(ArNacnac-H)Mg(TMC)2] (Ar=Xyl or Dip), were similarly synthesised and crystallographically characterized. Computational studies have been employed to investigate the mechanisms of the two observed reaction types, which appear dependent on the substitution pattern of the magnesium(I) compound, and the stoichiometric equivalents of TMC used in the reactions.

KW - ethylene

KW - low oxidation state

KW - magnesium(I)

KW - reductive coupling

UR - http://www.scopus.com/inward/record.url?scp=85090484476&partnerID=8YFLogxK

U2 - 10.1002/chem.202002380

DO - 10.1002/chem.202002380

M3 - Article

AN - SCOPUS:85090484476

SN - 1521-3765

VL - 26

SP - 14665

EP - 14670

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 64

ER -

Activation of Ethylene by N-Heterocyclic Carbene Coordinated Magnesium(I) Compounds

Abstract

Keywords

Access to Document

Other files and links

Australian Synchrotron

Cite this

Activation of Ethylene by N-Heterocyclic Carbene Coordinated Magnesium(I) Compounds

Abstract

Keywords

Access to Document

Other files and links

Equipment

Australian Synchrotron

Cite this