Exogenous nitrile substrate hydroxylation by a new dicopper-hydroperoxide complex.
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.
Li
Lei
L
Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA.
Narducci Sarjeant
Amy A
AA
Vance
Michael A
MA
Zakharov
Lev N
LN
Rheingold
Arnold L
AL
Solomon
Edward I
EI
Karlin
Kenneth D
KD
D032701:Biomimetics; D003300:Copper; D006861:Hydrogen Peroxide; D006900:Hydroxylation; D009570:Nitriles / Q000737:chemistry*
D009570:Nitriles; D003300:Copper; D006861:Hydrogen Peroxide; C030973:cupric oxide