Variable coordination of amine functionalised N-heterocyclic carbene ligands to Ru, Rh and Ir: C-H and N-H activation and catalytic transfer hydrogenation

Dalton Trans. 2011 Oct 14;40(38):9722-30. doi: 10.1039/c1dt10753d. Epub 2011 Aug 22.

Abstract

Chelating amine and amido complexes of late transition metals are highly valuable bifunctional catalysts in organic synthesis, but complexes of bidentate amine-NHC and amido-NHC ligands are scarce. Hence, we report the reactions of a secondary-amine functionalised imidazolium salt 2a and a primary-amine functionalised imidazolium salt 2b with [(p-cymene)RuCl(2)](2) and [Cp*MCl(2)](2) (M = Rh, Ir). Treating 2a with [Cp*MCl(2)](2) and NaOAc gave the cyclometallated compounds Cp*M(C,C)I (M = Rh, 3; M = Ir, 4), resulting from aromatic C-H activation. In contrast, treating 2b with [(p-cymene)RuCl(2)](2), Ag(2)O and KI gave the amine-NHC complex [(p-cymene)Ru(C,NH(2))I]I (5). The reaction of 2b with [Cp*MCl(2)](2) (M = Rh, Ir), NaO(t)Bu and KI gave the amine-NHC complex [Cp*Rh(NH(2))I]I (6) or the amido-NHC complex Cp*Ir(C,NH)I (7); both protonation states of the Ir complex could be accessed: treating 7 with trifluoroacetic acid gave the amine-NHC complex [Cp*Ir(C,NH(2))I][CF(3)CO(2)] (8). These are the first primary amine- or amido-NHC complexes of Rh and Ir. Solid-state structures of the complexes 3-8 have been determined by single crystal X-ray diffraction. Complexes 5, 6 and 7 are pre-catalysts for the catalytic transfer hydrogenation of acetophenone to 1-phenylethanol, with ruthenium complex 5 demonstrating especially high reactivity.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amides / chemistry
  • Amines / chemistry*
  • Catalysis
  • Chelating Agents / chemical synthesis*
  • Chelating Agents / chemistry
  • Crystallography, X-Ray
  • Heterocyclic Compounds / chemistry*
  • Hydrogenation
  • Iridium / chemistry
  • Ligands
  • Methane / analogs & derivatives*
  • Methane / chemistry
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry
  • Rhenium / chemistry
  • Ruthenium / chemistry
  • Stereoisomerism

Substances

  • Amides
  • Amines
  • Chelating Agents
  • Heterocyclic Compounds
  • Ligands
  • Organometallic Compounds
  • carbene
  • Iridium
  • Rhenium
  • Ruthenium
  • Methane