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Published on: July 27, 2022
Hydrogen activation by high-valent oxo-molybdenum(VI) and -rhenium(VII) and -(V) compounds
Patrícia M Reis1, Paulo Jorge Costa, Carlos C Romão
1Instituto de Tecnologia Química e Biológica da Universidade Nova de Lisboa, Quinta do Marquês, EAN, Apt. 127, 2781-901, Oeiras, Portugal.
Abstract:
The high-valent oxo-molybdenum(VI) and -rhenium(VII) and -(V) derivatives MoO2Cl2, ReCH3O3 (MTO) and ReIO2(PPh3)2 catalyze the selective hydrogenation of alkynes to alkenes at 80 degrees C under 40 atm of pressure. The reduction of sulfoxides to sulfides has also been performed by oxo-rhenium and -molybdenum complexes using hydrogen as a reducing agent. Activation of hydrogen by MoO2Cl2 and MoO2(S2CNEt2)2 was shown by means of DFT calculations to proceed by H-H addition to the Mo=O bond, followed by hydride migration to yield a water complex.
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