Hydrogen activation by high-valent oxo-molybdenum(VI) and -rhenium(VII) and -(V) compounds.
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.
Reis
Patrícia M
PM
Instituto de Tecnologia Química e Biológica da Universidade Nova de Lisboa, Quinta do Marquês, EAN, Apt. 127, 2781-901, Oeiras, Portugal.
Costa
Paulo Jorge
PJ
Romão
Carlos C
CC
Fernandes
José A
JA
Calhorda
Maria José
MJ
Royo
Beatriz
B