N-heterocyclic carbene complexes of copper(i) thiocyanate: synthesis and structural characterization

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Abstract

The synthesis and characterization of three N-heterocyclic carbene (NHC) complexes of copper(I) thiocyanate [Cu(IMes)(NCS)]2 (1), [Cu(IXy)(NCS)]2 (2), and [Cu(IPr)(NCS)] (3) [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] are described. Single crystal diffraction and IR spectroscopy shows that reaction of one equivalent of sodium thiocyanate with [Cu(NHC)Cl] results in the formation of solid-state centrosymmetric dimers for 1 and 2 with bridging thiocyanate ligands bound through both N and S. In contrast, the equivalent reaction with IPr gives a monomeric species with N bound thiocyanate. In the solution state, all the structures of complexes 1-3 would appear to be monomeric, as evidenced by both solution state FT-IR and 13C NMR spectroscopic studies. In addition the precursor to complex 2 [Cu(IXy)Cl] (4) was structurally characterized by X-ray diffraction revealing a one-dimensional chain structure that propagates through C-H···Cl intermolecular interactions with both methyl and aromatic hydrogen atoms.

LanguageEnglish
Pages926-930
Number of pages5
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume640
Issue number5
DOIs
Publication statusPublished - 10 Mar 2014

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Copper
Dimers
Hydrogen
Infrared spectroscopy
Diffraction
Nuclear magnetic resonance
Single crystals
Ligands
X ray diffraction
Atoms
thiocyanate
carbene
1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene
1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene
sodium thiocyanate

Keywords

  • carbene ligand
  • copper
  • crystal structure
  • NMR spectroscopy
  • thiocyanate

Cite this

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title = "N-heterocyclic carbene complexes of copper(i) thiocyanate: synthesis and structural characterization",
abstract = "The synthesis and characterization of three N-heterocyclic carbene (NHC) complexes of copper(I) thiocyanate [Cu(IMes)(NCS)]2 (1), [Cu(IXy)(NCS)]2 (2), and [Cu(IPr)(NCS)] (3) [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] are described. Single crystal diffraction and IR spectroscopy shows that reaction of one equivalent of sodium thiocyanate with [Cu(NHC)Cl] results in the formation of solid-state centrosymmetric dimers for 1 and 2 with bridging thiocyanate ligands bound through both N and S. In contrast, the equivalent reaction with IPr gives a monomeric species with N bound thiocyanate. In the solution state, all the structures of complexes 1-3 would appear to be monomeric, as evidenced by both solution state FT-IR and 13C NMR spectroscopic studies. In addition the precursor to complex 2 [Cu(IXy)Cl] (4) was structurally characterized by X-ray diffraction revealing a one-dimensional chain structure that propagates through C-H···Cl intermolecular interactions with both methyl and aromatic hydrogen atoms.",
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author = "Dodds, {Christopher A.} and Alan Kennedy",
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TY - JOUR

T1 - N-heterocyclic carbene complexes of copper(i) thiocyanate

T2 - Zeitschrift fur Anorganische und Allgemeine Chemie

AU - Dodds, Christopher A.

AU - Kennedy, Alan

PY - 2014/3/10

Y1 - 2014/3/10

N2 - The synthesis and characterization of three N-heterocyclic carbene (NHC) complexes of copper(I) thiocyanate [Cu(IMes)(NCS)]2 (1), [Cu(IXy)(NCS)]2 (2), and [Cu(IPr)(NCS)] (3) [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] are described. Single crystal diffraction and IR spectroscopy shows that reaction of one equivalent of sodium thiocyanate with [Cu(NHC)Cl] results in the formation of solid-state centrosymmetric dimers for 1 and 2 with bridging thiocyanate ligands bound through both N and S. In contrast, the equivalent reaction with IPr gives a monomeric species with N bound thiocyanate. In the solution state, all the structures of complexes 1-3 would appear to be monomeric, as evidenced by both solution state FT-IR and 13C NMR spectroscopic studies. In addition the precursor to complex 2 [Cu(IXy)Cl] (4) was structurally characterized by X-ray diffraction revealing a one-dimensional chain structure that propagates through C-H···Cl intermolecular interactions with both methyl and aromatic hydrogen atoms.

AB - The synthesis and characterization of three N-heterocyclic carbene (NHC) complexes of copper(I) thiocyanate [Cu(IMes)(NCS)]2 (1), [Cu(IXy)(NCS)]2 (2), and [Cu(IPr)(NCS)] (3) [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] are described. Single crystal diffraction and IR spectroscopy shows that reaction of one equivalent of sodium thiocyanate with [Cu(NHC)Cl] results in the formation of solid-state centrosymmetric dimers for 1 and 2 with bridging thiocyanate ligands bound through both N and S. In contrast, the equivalent reaction with IPr gives a monomeric species with N bound thiocyanate. In the solution state, all the structures of complexes 1-3 would appear to be monomeric, as evidenced by both solution state FT-IR and 13C NMR spectroscopic studies. In addition the precursor to complex 2 [Cu(IXy)Cl] (4) was structurally characterized by X-ray diffraction revealing a one-dimensional chain structure that propagates through C-H···Cl intermolecular interactions with both methyl and aromatic hydrogen atoms.

KW - carbene ligand

KW - copper

KW - crystal structure

KW - NMR spectroscopy

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