title: Steric effects in the aerobic oxidation of pi-allylnickel(II) complexes with N-heterocyclic carbenes.
abstract: Pi-allylchloro(NHC)nickel(II) complexes were synthesized and their reactions with O2 were studied. Ligand steric effects were found to determine the difference between rapid oxidation of the allyl group to produce bis-mu-hydroxonickel complexes and no observable reaction. The ability of the metal-NHC bond to rotate correlates with the ability of the complex to react with O2. In the limiting cases, conformationally restricted complexes are stable to O2 and complexes with rapid Ni-NHC bond rotation react rapidly with O2. Complexes with intermediate conformational flexibility were found to exhibit lesser reactivity with O2. On the basis of the observed inertness of complexes with saddle-shaped ligands to O2, we propose the adoption of a nonplanar geometry upon reaction with O2 to be required. The issue of conformational flexibility versus rigidity is expected to directly impact the catalytic behavior of metal-NHC complexes.
authors.affiliation: Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
authors.forename: Benjamin R
authors.initials: BR
authors.lastname: Dible
authors.forename: Matthew S
authors.initials: MS
authors.lastname: Sigman
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006838:Hydrocarbons / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D000498:Allyl Compounds; D006571:Heterocyclic Compounds; D006838:Hydrocarbons; D009942:Organometallic Compounds; C030011:carbene; D009532:Nickel; D008697:Methane