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; Beatriz Royo

doi:10.1039/B719375K

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Dalton Transactions

Issue 13, 2008

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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

Dalton Trans., 2008, 1727-1733

DOI: 10.1039/B719375K
Received 17 Dec 2007, Accepted 08 Feb 2008
First published on the web 27 Feb 2008

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Abstract
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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 Mo [double bond, length as m-dash] O bond, followed by hydride migration to yield a water complex.

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Coordinates of the DFT optimized compounds
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Patrícia M. Reis
Paulo Jorge Costa
Carlos C. Romão
José A. Fernandes
Maria José Calhorda
Beatriz Royo

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Dalton Transactions

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

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