Reactions of (imidazol-2-ylidene)silver(I) chlorides with group 4 metal containing Lewis acids

D. Hollmann, A.R. Kennedy, M.D. Spicer, T. Ramnial, J.C. Clyburne, C.D. Abernethy

Research output: Contribution to journalArticle

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Abstract

The reactivity of the monomeric N-heterocyclic carbene silver(I) complexes, 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene-silver(I) chloride ([Ag(IMes)Cl], 1) and 1,3-bis-(4-bromo-2,6-dimethylphenyl)imidazol-2-ylidene-silver(I) chloride ([Ag(IMeSBr)Cl], 2), toward the group 4 metal containing Lewis acids, TiCl4 and (eta(5)-C5H5)ZrCl3](-) in dichloromethane was investigated. Instead of the expected transfer of the A-heterocyclic carbene to the Lewis acidic metal centers with accompanying precipitation of AgCl, chloride transfer occurred leading to the formation of the salts, [Ag(IMeS)(2)](+)[(TiCl3)(2)(mu(2)-Cl)(3)](-)(_) (3) and [Ag(IMes(Br))(2)(+)[{(eta(5)-C5H5)ZrCl}(2)(mu(2)-Cl)(3)(-) (4). The structure of the [Ag(IMes(Br))(2)](+) cation in 4 is significantly distorted in the solid state by interactions between the para-Br atoms of the IMeSBr ligands and chloride ligands of the anions.
Original languageEnglish
Pages (from-to)5346-5352
Number of pages6
JournalJournal of Organometallic Chemistry
Volume690
Issue number23
DOIs
Publication statusPublished - 15 Nov 2005

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Lewis Acids
imidazoles
Silver
Chlorides
Metals
chlorides
silver
Ligands
acids
Acids
Methylene Chloride
carbenes
metals
Anions
Cations
Salts
Dichloromethane
ligands
Negative ions
Positive ions

Keywords

  • N-heterocyclic carbene
  • silver
  • titanium
  • zirconium
  • poly-nuclear transition metal ions

Cite this

Hollmann, D. ; Kennedy, A.R. ; Spicer, M.D. ; Ramnial, T. ; Clyburne, J.C. ; Abernethy, C.D. / Reactions of (imidazol-2-ylidene)silver(I) chlorides with group 4 metal containing Lewis acids. In: Journal of Organometallic Chemistry. 2005 ; Vol. 690, No. 23. pp. 5346-5352.
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Reactions of (imidazol-2-ylidene)silver(I) chlorides with group 4 metal containing Lewis acids. / Hollmann, D.; Kennedy, A.R.; Spicer, M.D.; Ramnial, T.; Clyburne, J.C.; Abernethy, C.D.

In: Journal of Organometallic Chemistry, Vol. 690, No. 23, 15.11.2005, p. 5346-5352.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reactions of (imidazol-2-ylidene)silver(I) chlorides with group 4 metal containing Lewis acids

AU - Hollmann, D.

AU - Kennedy, A.R.

AU - Spicer, M.D.

AU - Ramnial, T.

AU - Clyburne, J.C.

AU - Abernethy, C.D.

PY - 2005/11/15

Y1 - 2005/11/15

N2 - The reactivity of the monomeric N-heterocyclic carbene silver(I) complexes, 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene-silver(I) chloride ([Ag(IMes)Cl], 1) and 1,3-bis-(4-bromo-2,6-dimethylphenyl)imidazol-2-ylidene-silver(I) chloride ([Ag(IMeSBr)Cl], 2), toward the group 4 metal containing Lewis acids, TiCl4 and (eta(5)-C5H5)ZrCl3](-) in dichloromethane was investigated. Instead of the expected transfer of the A-heterocyclic carbene to the Lewis acidic metal centers with accompanying precipitation of AgCl, chloride transfer occurred leading to the formation of the salts, [Ag(IMeS)(2)](+)[(TiCl3)(2)(mu(2)-Cl)(3)](-)(_) (3) and [Ag(IMes(Br))(2)(+)[{(eta(5)-C5H5)ZrCl}(2)(mu(2)-Cl)(3)(-) (4). The structure of the [Ag(IMes(Br))(2)](+) cation in 4 is significantly distorted in the solid state by interactions between the para-Br atoms of the IMeSBr ligands and chloride ligands of the anions.

AB - The reactivity of the monomeric N-heterocyclic carbene silver(I) complexes, 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene-silver(I) chloride ([Ag(IMes)Cl], 1) and 1,3-bis-(4-bromo-2,6-dimethylphenyl)imidazol-2-ylidene-silver(I) chloride ([Ag(IMeSBr)Cl], 2), toward the group 4 metal containing Lewis acids, TiCl4 and (eta(5)-C5H5)ZrCl3](-) in dichloromethane was investigated. Instead of the expected transfer of the A-heterocyclic carbene to the Lewis acidic metal centers with accompanying precipitation of AgCl, chloride transfer occurred leading to the formation of the salts, [Ag(IMeS)(2)](+)[(TiCl3)(2)(mu(2)-Cl)(3)](-)(_) (3) and [Ag(IMes(Br))(2)(+)[{(eta(5)-C5H5)ZrCl}(2)(mu(2)-Cl)(3)(-) (4). The structure of the [Ag(IMes(Br))(2)](+) cation in 4 is significantly distorted in the solid state by interactions between the para-Br atoms of the IMeSBr ligands and chloride ligands of the anions.

KW - N-heterocyclic carbene

KW - silver

KW - titanium

KW - zirconium

KW - poly-nuclear transition metal ions

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