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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Dalton Trans., 2008, 1727 - 1733, DOI: 10.1039/b719375k

Hydrogen activation by high-valent oxo-molybdenum(VI) and -rhenium(VII) and -(V) compounds

Patrícia M. Reis, Paulo Jorge Costa, Carlos C. Romão, José A. Fernandes, Maria José Calhorda and Beatriz Royo

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 °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 MoO bond, followed by hydride migration to yield a water complex.

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