Because these mononuclear metal-dioxygen (M-O-2) adducts are implicated as key intermediates in dioxygen activation reactions catalyzed by metalloenzymes, studies of the structural and spectroscopic properties and reactivities of synthetic biomimetic analogues additional hints Ibrutinib Src inhibitor of these spedes have aided Inhibitors,Modulators,Libraries our understanding of their biological chemistry. One particularly versatile class of biomimetic coordination complexes for studying dioxygen activation Inhibitors,Modulators,Libraries by metal complexes is M-O-2 complexes bearing the macrocyclic N-tetramethylated cyclam (TMC) ligand.
This Account describes the synthesis, structural and spectroscopic characterization, and reactivity Inhibitors,Modulators,Libraries studies of M-O-2 complexes bearing tetraazamacrocyclic n-TMC ligands, where M = Cr, Mn, Fe, Co, and Ni and n=12, Inhibitors,Modulators,Libraries 13, and 14, based on recent results from our laboratory.
Inhibitors,Modulators,Libraries We have used various spectroscopic techniques, including resonance Raman and X-ray absorption spectroscopy, and density functional theory (DFT) calculations to characterize several novel metal-O-2 complexes. Notably, X-ray crystal structures had shown that these Inhibitors,Modulators,Libraries complexes are end-on metal-superoxo and side-on metal-peroxo species. The metal ions and the ring size of the macrocyclic TMC ligands control Inhibitors,Modulators,Libraries the geometric and electronic structures of the metal-O-2 complexes, resulting in the end-on metal-superoxo versus side-on metal-peroxo structures. Reactivity studies performed with the isolated metal-superoxo complexes reveal that they can conduct electrophilic reactions such as oxygen atom transfer and C-H bond activation of organic substrates.
The metal-peroxo complexes are active oxidants in nucleophilic reactions, such Inhibitors,Modulators,Libraries as aldehyde deformylation. We also demonstrate a complete intermolecular O-2-transfer from metal(III)-peroxo complexes to a Mn(II) complex. The results presented in this Inhibitors,Modulators,Libraries Account Inhibitors,Modulators,Libraries show the significance of metal ions and supporting ligands in tuning the geometric and electronic structures and reactivities of the metal-O-2 intermediates that are relevant in biology and in biomimetic reactions.”
“The development of innovative metal catalysis for selective bond formation is an important task in organic chemistry. The group 13 metal indium is appealing for catalysis because indium-based reagents are minimally toxic, selective, and tolerant toward various functional groups.
Among elements in this group, the most stable oxidation state is typically +3, but in molecules with larger group 13 atoms, the chemistry of the +1 investigate this site oxidation state is selleck chemicals also important. The use of indium(III) compounds in organic synthesis has been well-established as Lewis add catalysts including asymmetric versions thereof.