Ruthenium Catalyzed Hydrogenation of Aldehyde with Synthesis Gas

The hydrogenation of aldehyde utilizing synthesis gas as a dihydrogen source was examined with various ruthenium catalysts, among which Ru–cyclopentadienone complexes (Shvo-type catalysts) exhibited higher activity than others. DFT calculations proved that the exchange of coordinated carbon monoxide by dihydrogen is relatively preferable in Shvo-type catalysts compared to others, which is a pre-equilibrium for the generation of the hydrogenation-active species

Tandem Hydroformylation/Hydrogenation of Alkenes to Normal Alcohols Using Rh/Ru Dual Catalyst or Ru Single Component Catalyst

The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and ³¹P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H₂/CO pressure clarified different kinetics from the hydrogenation under H₂ and gave a clue to design more active hydrogenation catalysts under H₂/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported

Tandem Hydroformylation/Hydrogenation of Alkenes to Normal Alcohols Using Rh/Ru Dual Catalyst or Ru Single Component Catalyst

The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and ³¹P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H₂/CO pressure clarified different kinetics from the hydrogenation under H₂ and gave a clue to design more active hydrogenation catalysts under H₂/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported

Tandem Hydroformylation/Hydrogenation of Alkenes to Normal Alcohols Using Rh/Ru Dual Catalyst or Ru Single Component Catalyst

The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and ³¹P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H₂/CO pressure clarified different kinetics from the hydrogenation under H₂ and gave a clue to design more active hydrogenation catalysts under H₂/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported

Photoprecursor Approach Enables Preparation of Well-Performing Bulk-Heterojunction Layers Comprising a Highly Aggregating Molecular Semiconductor

Active-layer morphology critically affects the performance of organic photovoltaic cells, and thus its optimization is a key toward the achievement of high-efficiency devices. However, the optimization of active-layer morphology is sometimes challenging because of the intrinsic properties of materials such as strong self-aggregating nature or low miscibility. This study postulates that the “photoprecursor approach” can serve as an effective means to prepare well-performing bulk-heterojunction (BHJ) layers containing highly aggregating molecular semiconductors. In the photoprecursor approach, a photoreactive precursor compound is solution-deposited and then converted in situ to a semiconducting material. This study employs 2,6-di­(2-thienyl)­anthracene (DTA) and [6,6]-phenyl-C₇₁-butyric acid methyl ester as p- and n-type materials, respectively, in which DTA is generated by the photoprecursor approach from the corresponding α-diketone-type derivative DTADK. When only chloroform is used as a cast solvent, the photovoltaic performance of the resulting BHJ films is severely limited because of unfavorable film morphology. The addition of a high-boiling-point cosolvent, <i>o</i>-dichlorobenzene (<i>o</i>-DCB), to the cast solution leads to significant improvement such that the resulting active layers afford up to approximately 5 times higher power conversion efficiencies. The film structure is investigated by two-dimensional grazing-incident wide-angle X-ray diffraction, atomic force microscopy, and fluorescence microspectroscopy to demonstrate that the use of <i>o</i>-DCB leads to improvement in film crystallinity and increase in charge-carrier generation efficiency. The change in film structure is assumed to originate from dynamic molecular motion enabled by the existence of solvent during the in situ photoreaction. The unique features of the photoprecursor approach will be beneficial in extending the material and processing scopes for the development of organic thin-film devices