N-heterocyclic-carbene-induced monomerization of sterically encumbered dialkylmagnesium and dialkylmanganese polymers

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Abstract

The sterically encumbered polymeric dialkyl complexes [M(CH2SiMe3)(2)](infinity) [M = Mg, Mn-II] were deaggregated by the potent two-electron sigma-donor, 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr), to yield the first examples of the monomeric three-coordinate [M(CH2SiMe3)(2)]center dot donor complexes [M = Mg (1); Mn (2)]. Similarly, monomeric three-coordinate species M[CH(SiMe3)(2)](2)center dot IPr [M = Mg, (3); Mn, (4)] were obtained from the bulkier disilyl-substituted alkyl [CH-(SiMe3)(2)] congeners M[CH(SiMe3)(2)](2)center dot ether by displacement of the ether by IPr. Complexes 1-4, which represent rare examples of N-heterocyclic-carbene-stabilized dialkylmagnesium and dialkylmanganese species, were crystallographically characterized; the diamagnetic magnesium complexes were also characterized in an arene solution by H-1 and C-13 NMR spectroscopy.

Original languageEnglish
Pages (from-to)4675-4679
Number of pages5
JournalEuropean Journal of Inorganic Chemistry
Issue number30
DOIs
Publication statusPublished - Oct 2011

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Ether
Polymers
Magnesium
Nuclear magnetic resonance spectroscopy
Electrons
carbene
1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene

Keywords

  • alkyl ligands
  • magnesium
  • manganese
  • N-heterocyclic carbenes
  • structure elucidation
  • tertiary phosphine adducts
  • structural characterization
  • alkyl complexes
  • x-ray
  • ligands
  • potassium

Cite this

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title = "N-heterocyclic-carbene-induced monomerization of sterically encumbered dialkylmagnesium and dialkylmanganese polymers",
abstract = "The sterically encumbered polymeric dialkyl complexes [M(CH2SiMe3)(2)](infinity) [M = Mg, Mn-II] were deaggregated by the potent two-electron sigma-donor, 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr), to yield the first examples of the monomeric three-coordinate [M(CH2SiMe3)(2)]center dot donor complexes [M = Mg (1); Mn (2)]. Similarly, monomeric three-coordinate species M[CH(SiMe3)(2)](2)center dot IPr [M = Mg, (3); Mn, (4)] were obtained from the bulkier disilyl-substituted alkyl [CH-(SiMe3)(2)] congeners M[CH(SiMe3)(2)](2)center dot ether by displacement of the ether by IPr. Complexes 1-4, which represent rare examples of N-heterocyclic-carbene-stabilized dialkylmagnesium and dialkylmanganese species, were crystallographically characterized; the diamagnetic magnesium complexes were also characterized in an arene solution by H-1 and C-13 NMR spectroscopy.",
keywords = "alkyl ligands, magnesium, manganese, N-heterocyclic carbenes, structure elucidation, tertiary phosphine adducts, structural characterization, alkyl complexes, x-ray, ligands, potassium",
author = "Alan Kennedy and Jan Klett and Stuart Robertson and Robert Mulvey",
year = "2011",
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doi = "10.1002/ejic.201100595",
language = "English",
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AU - Klett, Jan

AU - Robertson, Stuart

AU - Mulvey, Robert

PY - 2011/10

Y1 - 2011/10

N2 - The sterically encumbered polymeric dialkyl complexes [M(CH2SiMe3)(2)](infinity) [M = Mg, Mn-II] were deaggregated by the potent two-electron sigma-donor, 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr), to yield the first examples of the monomeric three-coordinate [M(CH2SiMe3)(2)]center dot donor complexes [M = Mg (1); Mn (2)]. Similarly, monomeric three-coordinate species M[CH(SiMe3)(2)](2)center dot IPr [M = Mg, (3); Mn, (4)] were obtained from the bulkier disilyl-substituted alkyl [CH-(SiMe3)(2)] congeners M[CH(SiMe3)(2)](2)center dot ether by displacement of the ether by IPr. Complexes 1-4, which represent rare examples of N-heterocyclic-carbene-stabilized dialkylmagnesium and dialkylmanganese species, were crystallographically characterized; the diamagnetic magnesium complexes were also characterized in an arene solution by H-1 and C-13 NMR spectroscopy.

AB - The sterically encumbered polymeric dialkyl complexes [M(CH2SiMe3)(2)](infinity) [M = Mg, Mn-II] were deaggregated by the potent two-electron sigma-donor, 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr), to yield the first examples of the monomeric three-coordinate [M(CH2SiMe3)(2)]center dot donor complexes [M = Mg (1); Mn (2)]. Similarly, monomeric three-coordinate species M[CH(SiMe3)(2)](2)center dot IPr [M = Mg, (3); Mn, (4)] were obtained from the bulkier disilyl-substituted alkyl [CH-(SiMe3)(2)] congeners M[CH(SiMe3)(2)](2)center dot ether by displacement of the ether by IPr. Complexes 1-4, which represent rare examples of N-heterocyclic-carbene-stabilized dialkylmagnesium and dialkylmanganese species, were crystallographically characterized; the diamagnetic magnesium complexes were also characterized in an arene solution by H-1 and C-13 NMR spectroscopy.

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KW - manganese

KW - N-heterocyclic carbenes

KW - structure elucidation

KW - tertiary phosphine adducts

KW - structural characterization

KW - alkyl complexes

KW - x-ray

KW - ligands

KW - potassium

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