TY - JOUR
T1 - 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
AU - Simonovic, Stevan
AU - Whitwood, Adrian C.
AU - Clegg, William
AU - Harrington, Ross W.
AU - Hursthouse, Michael B.
AU - Male, Louise
AU - Douthwaite, Richard E.
PY - 2009/5
Y1 - 2009/5
N2 - 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)
AB - 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)
KW - Carbene ligands
KW - Copper
KW - Homogeneous catalysis
KW - Mixed-valence compounds
KW - Cluster compounds
KW - CATALYZED CONJUGATE ADDITION
KW - ASYMMETRIC ALLYLIC ALKYLATION
KW - RING-OPENING POLYMERIZATION
KW - SCHIFF-BASE LIGANDS
KW - ALKOXY-NHC LIGANDS
KW - ALPHA-AMINO-ACIDS
KW - X-RAY-STRUCTURE
KW - ENANTIOSELECTIVE SYNTHESIS
KW - OLEFIN METATHESIS
KW - GRIGNARD-REAGENTS
UR - http://www.scopus.com/inward/record.url?scp=66149163227&partnerID=8YFLogxK
U2 - 10.1002/ejic.200801152
DO - 10.1002/ejic.200801152
M3 - Article
SN - 1434-1948
SP - 1786
EP - 1795
JO - EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
JF - EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
IS - 13
ER -