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New Insights into the Mechanism of Hydroperoxide Activation by Investigation of Dynamic Processes in the Coordination Sphere of Seven‐Coordinated Molybdenum Peroxo Complexes
Author(s) -
Hroch Angelika,
Gemmecker Gerd,
Thiel Werner R.
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200005)2000:5<1107::aid-ejic1107>3.0.co;2-e
Subject(s) - chemistry , molybdenum , dissociation (chemistry) , chelation , catalysis , ligand (biochemistry) , ammonia , coordination sphere , photochemistry , transition metal dioxygen complex , combinatorial chemistry , inorganic chemistry , organic chemistry , ion , cobalt , biochemistry , receptor
Seven‐coordinated molybdenum oxobisperoxo complexes with chelate nitrogen donors like pyrazolylpyridines are catalysts for the epoxidation of olefins. An NMR spectroscopic and quantumchemical study on the fluxionality of the chelate ligand proves that during this process partial ligand dissociation takes place. This gave rise to a detailed theoretical study on the activation of CH 3 OOH at the model complex (NH 3 ) 2 MoO(O 2 ) 2 including dissociation of one of the ammonia ligands and proton transfer from the hydroperoxide to one of the peroxo ligands.