Satoshi Muratsugu

We synthesized ferrocene-attached dimethyldihydropyrene (DHP) derivatives and investigated their photochemical and redox behaviors. For bis(ferrocenylethynyl)dimethyldihydropyrene (1), reversible photoisomerization between the closed DHP form (1c) and the open CPD form (1o) occurred in high yields upon alternate irradiation of visible (578 nm) light and UV (303 nm) light, whereas no photoisomerization proceeded for bis(pentamethylferrocenylethynyl)dimethyldihydropyrene (2). 1 exhibited reversibl

A pincer-iridium complex bearing a Lewis-base-free X-type alumanyl ligand has been synthesized. X-ray diffraction, NMR and IR spectroscopy, as well as XANES analysis confirmed its tetrahydrido-Ir^V structure and Lewis acidity at the Al center as supported by DFT calculations. The resulting complex was applied as a catalyst for the transfer dehydrogenation of cyclooctane.

Selective catalysis is critical for the development of green chemical processes, and natural enzymes that possess specialized three-dimensional reaction pockets with catalytically active sites represent the most sophisticated systems for selective catalysis. A reaction space in an enzyme consists of an active metal center, functional groups for molecular recognition (such as amino acids), and a surrounding protein matrix to prepare the reaction pocket. The artificial design of such an integrated

The photochemical properties and the mixed-valence state of bis(ferrocenylethynyl)benzodimethyldihydropyrene (1) and other benzodimethyldihydropyrene (BzDHP) derivatives were investigated to understand the reversible photoswitching in the electronic communication of 1. Absorption spectra of 1 were characterized by UV/Vis spectroscopy and calculated by using time-dependent density functional theory (TD-DFT), and the d orbitals of the ferrocene (Fc) moieties were shown to contribute to the occupie

A SiO₂-supported molecularly imprinted Pd complex with SiO₂-matrix overlayers was prepared as a Suzuki cross-coupling catalyst. A ligand on the supported Pd complex was used as a molecular imprinting template to create the reaction space. The structures of the supported and molecularly imprinted Pd complexes on SiO₂ were determined by solid-state MAS ¹³C, ²⁹Si, and ³¹P NMR; diffuse reflectance UV/vis; XPS; and Pd K-edge XAFS. The

We synthesized a dithiolato-bridged heterometal trinuclear complex [{(eta(5)-C(5)Me(5))Rh(S(2)C(6)H(4))}(2)Mo(CO)(2)] (1) in which two rhodadithiolene complex units are bridged by a Mo(CO)(2) moiety. Complex 1 with a Rh(III)-Mo(0)-Rh(III) bond exhibits reversible one-step two-electron reduction with potential inversion. This redox process between 1 and 1(2-) accompanies a reversible structural change, which is an alternation in the CO coordination mode between semibridging and bridging. The grou

Decarbonylation-promoted Ru nanoparticle formation from Ru3(CO)12 on a basic K-doped Al2O3 surface was investigated by in situ FT-IR and in situ XAFS. Supported Ru3(CO)12 clusters on K-doped Al2O3 were converted stepwise to Ru nanoparticles, which catalyzed the selective hydrogenation of nitriles to the corresponding primary amines via initial decarbonylation, the nucleation of the Ru cluster core, and the growth of metallic Ru nanoparticles on the surface. As a result, small Ru nanoparticles, w

A non-solvated alkyl-substituted Al(I) anion dimer was synthesized by a reduction of haloalumane precursor using a mechanochemical method. The crystallographic and theoretical analysis revealed its structure and electronic properties. Experimental XPS analysis of the Al(I) anions with reference compounds revealed the lower Al 2p binding energy corresponds to the lower oxidation state of Al species. It should be emphasized that the experimentally obtained XPS binding energies were reproduced by d

A novel oxide-supported Ir dimer, which was found to be active for transfer hydrogenation of aromatic ketones, was prepared on a γ-Al(2)O(3) surface from an Ir dimer complex [Ir(2){η(5)-C(5)(CH(3))(5)}(2)(μ-CH(2))(2)] (Ir(2)) with an Ir=Ir bond. Detailed characterization of the γ-Al(2)O(3)-supported Ir dimer (Ir(2)/γ-Al(2)O(3)) revealed that the structure of Ir(2) consisted of an Ir dimer with an Ir-Ir bond attached to the γ-Al(2)O(3) surface by two bridged Ir-(OAl)(2)-Ir bonds. The supported Ir

Redox potential inversion was observed during the two-electron (2e−) reduction of two novel heterometal trinuclear complexes, [Co2Mo(η5-C5Me5)2(S2C6H4)2(CO)2] (1) and [Rh2Mo(η5-C5Me5)2(S2C6H4)2(CO)2] (2), the metalladithiolenes of which were found to communicate electronically via a Mo(CO)2 moiety through two Co/Rh–Mo bonds. The redox properties and structural changes associated with each complex were investigated. 1 showed both two-step one-electron (1e−) reductions with a normal-order redox po

A new molecularly imprinted Ru-porphyrin complex catalyst on a SiO2 support was designed, prepared, and characterized in a step-by-step manner for the C5[double bond, length as m-dash]C6 epoxidation of cholesterol derivatives. High chemoselectivity for the C5[double bond, length as m-dash]C6 epoxidation of cholesterol derivatives without protecting the 3-position OH group and other oxidizable functional groups was achieved on the molecularly imprinted catalyst.

Size-controlled Pt nanoparticles were prepared on multi-wall carbon nanotubes (MWCNTs) decorated with polypyrrole matrix overlayers and exhibited superior oxygen reduction reaction (ORR) performance as electrocatalysts. The copolymerization of a new Pt₄-pyrrole complex and pyrrole monomer in the presence of MWCNTs produced size-controlled Pt nanoparticles with diameters of 1.5 ± 0.5 nm. The present size-controlled Pt nanoparticles showed better durability than non-regulated Pt nanopar

A robust heterogeneous Mn catalyst for selective epoxidation was prepared by the attachment of a Mn4 oxonuclear complex [Mn4O2(CH3COO)7(bipy)2](ClO4)·3H2O (1) on SiO2 and the successive stacking of SiO2-matrix overlayers around a supported Mn cluster. The structures of supported Mn catalysts were characterized by means of FT-IR spectroscopy, diffuse-reflectance UV/vis spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and Mn K-edge X-ray absorption fine structure. A ligand excha

The role of Cr species on Cr- and Rh-incorporated ceria catalysts (Cr0.19Rh0.06CeOz), which exhibit reversible redox performances at a temperature less than 373 K, was investigated for NO reduction catalysis. The incorporation of the Cr species to Cr0.19Rh0.06CeOz produced dispersed Rh species, whereas only the Rh-incorporated ceria catalyst without Cr (Rh0.04CeOz) produced small Rh0 aggregation, as characterized by high-angle annular dark-field scanning transmission electron microscopy coupled