Issue 13, 2008
From the journal:

Dalton Transactions

Hydrogenactivation by high-valent oxo-molybdenum(vi) and -rhenium(vii) and -(v) compounds†

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

* Corresponding authors

a Instituto de Tecnologia Química e Biológica da Universidade Nova de Lisboa, Quinta do Marquês, EAN, Apt. 127, Oeiras, Portugal
E-mail: broyo@itqb.unl.pt
Fax: +351 214411277
Tel: +351 214469754

b Departamento de Química e Bioquímica, CQB, Faculdade de Ciências, Universidade de Lisboa, Lisboa, Portugal
E-mail: mjc@fc.ul.pt
Fax: +351 217 500 088
Tel: +351 217 500 196

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 °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.

Graphical abstract: Hydrogen activation by high-valent oxo-molybdenum(vi) and -rhenium(vii) and -(v) compounds

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Article information

DOI
https://doi.org/10.1039/B719375K
Article type
Paper
Submitted
17 Dec 2007
Accepted
08 Feb 2008
First published
27 Feb 2008

Dalton Trans., 2008, 1727-1733

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

P. M. Reis, P. J. Costa, C. C. Romão, J. A. Fernandes, M. J. Calhorda and B. Royo, Dalton Trans., 2008, 1727 DOI: 10.1039/B719375K

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