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Activation of Ethylene by N‐Heterocyclic Carbene Coordinated Magnesium(I) Compounds
Author(s) -
Yuvaraj K.,
Douair Iskander,
Maron Laurent,
Jones Cameron
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002380
Subject(s) - magnesium , ethylene , carbene , chemistry , stoichiometry , medicinal chemistry , coupling reaction , organic chemistry , catalysis
Reactions of a series of magnesium(I) compounds with ethylene, in the presence of an N‐heterocyclic carbene (NHC), have been explored. Treating [{( Mes Nacnac)Mg} 2 ] ( Mes Nacnac=[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, [{( Mes Nacnac)(TMC)Mg} 2 (μ‐C 4 H 8 )]. In contrast, when the reaction is repeated in the presence of three equivalents of TMC, a mixture of the β‐diketiminato magnesium ethyl, [( Mes Nacnac)(TMC)MgEt], and the NHC coordinated magnesium diamide, [( Mes Nacnac ‐H )Mg(TMC) 2 ], results. Four related products, [( Ar Nacnac)(TMC)MgEt] (Ar=2,6‐dimethylphenyl (Xyl) or 2,6‐diisopropylphenyl (Dip)) and [( Ar Nacnac ‐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.