Mechanistic studies of Hangman salophen-mediated activation of O-O bonds.
Stopped-flow kinetic studies of a HSX-Mn-SalophOMe (1) catalyst provide spectroscopic evidence for the direct generation of a manganese(V) oxo salophen from a manganese(III) perbenzoate. The O-O bond heterolysis reaction that produces the oxo is not facilitated by intramolecular proton transfer from the acid hanging group of the HSX platform. Instead, the hanging group stabilizes the catalyst against oxidative degradation and, consistent with recent predictions of theory, is geometrically matched to promote the end-on coordination of a H2O2 substrate prior to its oxidation at the manganese(V) oxo center.
Liu
Shih-Yuan
SY
Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
Soper
Jake D
JD
Yang
Jenny Y
JY
Rybak-Akimova
Elena V
EV
Nocera
Daniel G
DG
D002384:Catalysis; D007700:Kinetics; D008345:Manganese / Q000737:chemistry; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D012459:Salicylates / Q000737:chemistry*
D012459:Salicylates; C090416:salophen; D008345:Manganese; D010100:Oxygen