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Models for the active site of oxotransferases

To develop more sustainable catalytic processes in oxygenation chemistry, it is of great interest to allow for the use of molecular oxygen and in further consequence air as a benign alternative to other oxidants. For that goal, the preceding “activation” of dioxygen molecules at a catalyst is necessary. In our group we study such an activation of molecular oxygen at molybdenum metal sites as well as the reactivity of the resulting complexes.

Fig. 1: Synthesis of oxido-peroxido Mo(VI) complexes with O2.

Of special interest is the oxygen activation reactivity of Mo(IV)/Mo(VI) systems based on different iminophenolates, with emphasis on the identification and unequivocal structural elucidation of all involved species via NMR techniques and X-Ray crystallography to be able to predict and modify their reactivity.

Fig. 2: Crystal structures of various Mo complexes.

We furthermore test the complexes for their activity in the catalytic aerobic oxidation with phosphanes (PMe3 and PPh3) as model substrates to investigate structure related reactivity differences.

 

Fig. 3: Catalytic oxidation of phosphines with molecular oxygen.

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