Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

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Abstract

The synthesis and co-ordination chemistry of a new ‘bulky yet flexible’ N-heterocyclic carbene (“IPaul”) is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*OMe complexes.
LanguageEnglish
Number of pages10
JournalDalton Transactions
Early online date16 Jun 2016
DOIs
Publication statusE-pub ahead of print - 16 Jun 2016

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Ligands
Copper
Hydrosilylation
Iridium
Carbonyl compounds
Coordination Complexes
Nickel
Silver
Electronic properties
Transition metals
Conformations
X rays
carbene

Keywords

  • carbene
  • N-heterocyclic carbene
  • x-ray crystallography

Cite this

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title = "Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact",
abstract = "The synthesis and co-ordination chemistry of a new ‘bulky yet flexible’ N-heterocyclic carbene (“IPaul”) is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*OMe complexes.",
keywords = "carbene, N-heterocyclic carbene, x-ray crystallography",
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T1 - Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

AU - Shaw, Paul

AU - Kennedy, Alan R.

AU - Nelson, David J.

PY - 2016/6/16

Y1 - 2016/6/16

N2 - The synthesis and co-ordination chemistry of a new ‘bulky yet flexible’ N-heterocyclic carbene (“IPaul”) is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*OMe complexes.

AB - The synthesis and co-ordination chemistry of a new ‘bulky yet flexible’ N-heterocyclic carbene (“IPaul”) is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*OMe complexes.

KW - carbene

KW - N-heterocyclic carbene

KW - x-ray crystallography

UR - http://pubs.rsc.org/en/content/articlelanding/2016/dt/c6dt02100j#!divAbstract

U2 - 10.1039/C6DT02100J

DO - 10.1039/C6DT02100J

M3 - Article

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