Biocatalytic and Biomimetic Oxidations from an Industrial Perspective

Hydrogen-Atom Transfer from Transition Metal Hydroperoxides, Hydrogen Peroxide, and Alkyl Hydroperoxides to Superoxo and Oxo Metal Complexes

“…In chemically simpler, nonenzymatic systems, the mechanistic assignments are somewhat more straightforward. Superoxo, hydroperoxo, and high-valent oxo complexes of various transition metals have been generated and characterized both chemically and spectroscopically. − Such work with well-defined species provides solid mechanistic information about the reaction or specific intermediates under study. It also provides means to address the feasibility of similar chemistry in complex biological or industrial catalytic reactions, where various pathways or species may be obscured by the spectral and/or chemical complexity of the overall system.…”

Vanadium-Based, Extended Catalytic Lifetime Catechol Dioxygenases: Evidence for a Common Catalyst

“…Oxygen activation for selective oxidation reactions continues to be a central and challenging subject in catalysis. − In nature, the discovery of dioxygenase enzymes, that is, enzymes catalyzing the incorporation of both oxygen atoms of O 2 into substrates with no added protons or electrons, dates back to the 1950s with the discovery of oxygen incorporation into catechol by pyrocatechase of Pseudomonas sp . Since that time, mild, selective, and facile man-made dioxygenases have been the Holy Grail of biomimetic studies of oxidation catalysis …”

Development of a Theoretical Model of Nickel(II) Tris(oxime)amine Dichloride with Comparison to X-ray Crystallography and Vibrational Spectroscopy

“…9,10 Progress toward this kind of green chemistry, by the development of mass-efficient oxidants and reusable metal catalysts, is of great interest in the 21st century. 11,12 Nickel complexes that activate molecular oxygen are rare, due primarily to the relatively inaccessible higher oxidation states of nickel. However, oximates have been shown to lower the oxidation potential of nickel(II) and stabilize high-valent nickel complexes.…”

“…Our group has developed unique, oxygen-active nickel(II) complexes with tripodal amine ligands incorporating oxime functional groups; upon deprotonation of the oximes, catalytic aerobic oxidation of substrates such as methanol is observed. , Progress toward this kind of green chemistry, by the development of mass-efficient oxidants and reusable metal catalysts, is of great interest in the 21st century. , Nickel complexes that activate molecular oxygen are rare, due primarily to the relatively inaccessible higher oxidation states of nickel. However, oximates have been shown to lower the oxidation potential of nickel(II) and stabilize high-valent nickel complexes. − A theoretical model may bring tremendous insight into the electronic structure of this candidate oxygen activation catalyst and may be applied to experimentally inaccessible putative intermediates.…”