Synthesis of Copper(I) Complexes of N-Heterocyclic Carbene-Phenoxyimine/amine Ligands: Structures of Mononuclear Copper(II), Mixed-Valence Copper(I)/(II), and Copper(II) Cluster Complexes

Stevan Simonovic, Adrian C. Whitwood, William Clegg, Ross W. Harrington, Michael B. Hursthouse, Louise Male, Richard E. Douthwaite

Research output: Contribution to journalArticlepeer-review

Abstract

Copper(I) bromide complexes (2a and 2b) of NHC-phenolimine ligand precursors {3-[(1R,2R)-2-{[1-(3,5-di-tert-butyl-2-hydroxyphenyl)meth-(E)-ylidene]amino}cyclohexyl]-1-isopropyl-4-phenyl-3H-imidazol-1-ium bromide (1a) and 3-(1R,2R)-2-{[1-(2-hydroxyphenyl)meth-(E)-ylidene]amino}- cyclohexyl]-1-isopropyl-4-phenyl-3H-imidazol-1-ium bromide (1b), respectively} have been prepared. Complexes 2a and 2b exhibit copper coordination only through the carbene carbon atom (C) and do not spontaneously eliminate HBr to give additional phenoxyimine (NO) bonds, which is attributed to intramolecular hydrogen bonding. Crystallisation of 2a and 2b gives 2a' and 2b', respectively, that contain (C) copper(I) bromide and (NO)(2) copper(II) coordination. Complex 2b' also exhibits intermolecular CuIBr interactions giving a Cu2Br2 bridge that links two molecules of 2b' resulting in an ellipse motif. Reduction of the hgand precursor imine group of la allows synthesis of silver(I) and copper(I) NHCphenolamine complexes 6 and 7, respectively, that also retain the phenol hydrogen atom. Attempts to selectively prepare 2a' gave a copper(II) complex 9 that exhibits an (NO)(2)Cu-II structure with pendant in-ddazolium salt groups. Reaction between the silver(I) bromide derivative of la and CuCl2 center dot 2H(2)O gives a complex derived from a Cu-6(O)(OH)(4)Cl-3 core and two (NO) and one (CNO) ligands, respectively. The use of 2a and 7 as precatalysts for 1,4-conjugate addition to enones and aziridination of alkenes was studied, showing that, whilst both catalysts are active, enantioselectivities are low, which is attributed to the lack of Cu-(NO) coordination. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheirn, Germany, 2009)

Original languageEnglish
Pages (from-to)1786-1795
Number of pages10
JournalEUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Issue number13
DOIs
Publication statusPublished - May 2009

Keywords

  • Carbene ligands
  • Copper
  • Homogeneous catalysis
  • Mixed-valence compounds
  • Cluster compounds
  • CATALYZED CONJUGATE ADDITION
  • ASYMMETRIC ALLYLIC ALKYLATION
  • RING-OPENING POLYMERIZATION
  • SCHIFF-BASE LIGANDS
  • ALKOXY-NHC LIGANDS
  • ALPHA-AMINO-ACIDS
  • X-RAY-STRUCTURE
  • ENANTIOSELECTIVE SYNTHESIS
  • OLEFIN METATHESIS
  • GRIGNARD-REAGENTS

Cite this