title: Exogenous nitrile substrate hydroxylation by a new dicopper-hydroperoxide complex.
abstract: A dicopper(I)/phenol-ligand complex in RCN solvents reacts with O2 producing a mu-1,1-hydroperoxo dicopper(II) species. Subsequent thermal transformation results in nitrile hydroxylation and elimination of cyanide, as revealed by the isolation in comparable yields of (i) a cyanide-bridged tetranuclear cluster complex and (ii) benzaldehyde (for R = PhCH2); 18O labeling confirms that the PhC(O)H oxygen atom derives from O2.
authors.affiliation: Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA.
authors.forename: Lei
authors.initials: L
authors.lastname: Li
authors.forename: Amy A
authors.initials: AA
authors.lastname: Narducci Sarjeant
authors.forename: Michael A
authors.initials: MA
authors.lastname: Vance
authors.forename: Lev N
authors.initials: LN
authors.lastname: Zakharov
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D032701:Biomimetics; D003300:Copper; D006861:Hydrogen Peroxide; D006900:Hydroxylation; D009570:Nitriles / Q000737:chemistry*
chemical_list: D009570:Nitriles; D003300:Copper; D006861:Hydrogen Peroxide; C030973:cupric oxide