High-Density Formation of Ir/MoO Interface through Hybrid Clustering for Chemoselective Nitrostyrene Hydrogenation
Shun Hayashi1, Tetsuya Shishido2,3,4
1Division of Physical Sciences, Department of Science and Engineering, National Museum of Nature and Science, Ibaraki 305-0005, Japan.
Abstract:
To form high-density metal/oxide interfacial active sites, we developed a catalyst preparation method based on hybrid clustering. An iridium-molybdenum (Ir-Mo) hybrid clustering catalyst was prepared by using the hybrid cluster [(IrCp*)4Mo4O16] (Cp* = η5-C5Me5) as the precursor. The Ir-Mo hybrid clustering catalyst selectively reduced the nitro group in the hydrogenation of 4-nitrostyrene, whereas the coimpregnated Ir-Mo catalyst reduced both the nitro and vinyl groups nonselectively. The hybrid clustering catalyst also exhibited high selectivity, even at a high Ir loading (5 wt %), in contrast to Ir/MoO3, which exhibited high selectivity only at low Ir loadings (<0.3 wt %). In situ X-ray absorption spectroscopy analysis revealed that oxygen vacancies were formed at the Ir/MoO interface in the presence of H2. We concluded that a high-density Ir/MoO interface contributes to the preferential adsorption of nitro groups on vacant sites, promoting the selective hydrogenation of nitro groups.
Related Concept Videos
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Regioselectivity of Electrophilic Additions-Peroxide Effect
Radical Anti-Markovnikov Addition to Alkenes: Overview
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.


