Yoshiyuki Ogasawara

Highly Dispersed Ruthenium Hydroxide Supported on Titanium Oxide Effective for Liquid‐Phase Hydrogen‐Transfer Reactions

Supported ruthenium hydroxide catalysts (Ru(OH)(x)/support) were prepared with three different TiO(2) supports (anatase TiO(2) (TiO(2)(A), BET surface area: 316 m(2) g(-1)), anatase TiO(2) (TiO(2)(B), 73 m(2) g(-1)), and rutile TiO(2) (TiO(2)(C), 3.2 m(2) g(-1))), as well as an Al(2)O(3) support (160 m(2) g(-1)). Characterizations with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), and X-ray absorption fine structure (XAFS) showed the presence of monomeric ruthenium(III) hydroxide and polymeric ruthenium(III) hydroxide species. Judging from the coordination numbers of the nearest-neighbor Ru atoms and the intensities of the ESR signals, the amount of monomeric hydroxide species increased in the order of Ru(OH)(x)<Ru(OH)(x)/TiO(2)(C)<Ru(OH)(x)/Al(2)O(3)<Ru(OH)(x)/TiO(2)(B)<Ru(OH)(x)/TiO(2)(A). These supported ruthenium hydroxide catalysts, especially Ru(OH)(x)/TiO(2)(A), showed high catalytic activities and selectivities for liquid-phase hydrogen-transfer reactions, such as racemization of chiral secondary alcohols and the reduction of carbonyl compounds and allylic alcohols. The catalytic activities of Ru(OH)(x)/TiO(2)(A) for these hydrogen-transfer reactions were at least one order of magnitude higher than those of previously reported heterogeneous catalysts, such as Ru(OH)(x)/Al(2)O(3). These catalyses were truly heterogeneous, and the catalysts recovered after the reactions could be reused several times without loss of catalytic performance. The reaction rates monotonically increased with an increase in the amount of monomeric ruthenium hydroxide species, which suggests that the monomeric species are effective for these hydrogen-transfer reactions.

A supported rhodium hydroxide catalyst: preparation, characterization, and scope of the synthesis of primary amides from aldoximes or aldehydes.

A supported rhodium hydroxide catalyst, Rh(OH)(x)/Al(2)O(3) (x=3), is prepared by the reaction of Al(2)O(3) with RhCl(3) in an aqueous medium followed by treatment with NaOH. The Rh(III) hydroxide species is monomerically (or highly) dispersed on the Al(2)O(3) support. Rh(OH)(x)/Al(2)O(3) acts as a reusable heterogeneous catalyst in water, rather than in an explosive, hazardous, and carcinogenic organic solvent, for the synthesis of primary amides from aldoximes or aldehydes by an efficient sequential process of dehydration and rehydration. The dehydrative condensation of aldehydes and hydroxylamine is also promoted by the Rh(OH)(x)/Al(2)O(3) catalyst.

Green oxidative synthesis of primary amides from primary alcohols or aldehydes catalyzed by a cryptomelane-type manganese oxide-based octahedral molecular sieve, OMS-2

In this study, a new green synthetic route to primary amides, that is, aerobic oxidative amidation of primary alcohols or aldehydes with ammonia, has been developed. In the presence of a cryptomelane-type manganese oxide-based octahedral molecular sieve (OMS-2), various kinds of structurally diverse primary alcohols or aldehydes including aromatic, olefinic, heteroaromatic, and aliphatic ones can be converted into the corresponding primary amides in moderate to high yields (20 examples from primary alcohols and 11 examples from aldehydes). Furthermore, gram-scale amidation is also effective, and the analytically pure primary amides can easily be isolated. The present catalysis by OMS-2 is truly heterogeneous in nature, and the retrieved OMS-2 catalyst can be reused several times (at least 12 times for the amidation of 2-pyridinemethanol). Though the formation rates of the corresponding primary amide are gradually decreased by repeating reuse experiments, OMS-2 can be regenerated by calcination. The present OMS-2-catalyzed amidation of primary alcohols is composed of four relay steps: (i) oxidative dehydrogenation of primary alcohols, (ii) dehydrative condensation of aldehydes with ammonia, (iii) oxidative dehydrogenation of aldimines, and (iv) hydration of nitriles to form the corresponding primary amides. All steps (i)–(iv) can be promoted by the presence of OMS-2.

A Tin–Tungsten Mixed Oxide as an Efficient Heterogeneous Catalyst for CC Bond-Forming Reactions

The tin-tungsten mixed oxide prepared by the calcination of the tin-tungsten hydroxide precursor with a Sn/W molar ratio of 2 at 800 degrees C (SnW2-800) acts as an effective and reusable solid catalyst for C-C bond-forming reactions, such as the cyclization of citronellal, the Diels-Alder reaction, and the cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN). Various kinds of structurally diverse aliphatic, aromatic, and unsaturated, heteroatom-containing substrates could be converted into the desired products in high to excellent yields. The observed catalyses for these reactions were truly heterogeneous and the recovered catalyst could be reused several times without an appreciable loss of its high catalytic performance. The Brønsted acid sites generated on the aggregated polytungstate species on SnW2-800 likely play an important role in the C-C bond-forming reactions.

A new sealed lithium-peroxide battery with a co-doped Li2O cathode in a superconcentrated lithium bis(fluorosulfonyl)amide electrolyte.

We propose a new sealed battery operating on a redox reaction between an oxide (O2−) and a peroxide (O22−) with its theoretical specific energy of 2570 Wh kg−1 (897 mAh g−1, 2.87 V) and demonstrate that a Co-doped Li2O cathode exhibits a reversible capacity over 190 mAh g−1, a high rate capability, and a good cyclability with a superconcentrated lithium bis(fluorosulfonyl)amide electrolyte in acetonitrile. The reversible capacity is largely dominated by the O2−/O22− redox reaction between oxide and peroxide with some contribution of the Co2+/Co3+ redox reaction.

Molybdenum-doped α-MnO2 as an efficient reusable heterogeneous catalyst for aerobic sulfide oxygenation

Oxygenation of sulfides to sulfoxides and/or sulfones is an important transformation, and the development of efficient heterogeneous catalysts for oxygenation, which can utilize O2 as the terminal oxidant, is highly desired. In this study, we have successfully developed manganese oxide-based efficient heterogeneous catalysts for aerobic oxygenation of sulfides. Firstly, we prepared four kinds of manganese oxides possessing different crystal structures, such as α-MnO2, β-MnO2, γ-MnO2, and δ-MnO2, and their structure–activity relationships were examined for the aerobic oxygenation of thioanisole. Amongst them, α-MnO2 showed the best catalytic performance for the oxygenation. Moreover, α-MnO2 was highly stable during the catalytic oxygenation possibly due to the tunnel K+ ions. In order to further improve the catalytic performance of α-MnO2, substitutional doping of transition metal cations, such as Mo6+, V5+, Cr3+, and Cu2+, into the framework was carried out. Undoped α-MnO2 possessed a fibrous morphology. When high-valent transition metal cations were doped, especially Mo6+, the lengths of the fibers drastically shortened to form grain-like aggregates of ultrafine nanocrystals, resulting in an increase in specific surface areas and the numbers of catalytically active surface sites. In the presence of Mo6+-doped α-MnO2 (Mo–MnO2), various kinds of sulfides could efficiently be oxidized to the corresponding sulfoxides as the major products. The observed catalysis was truly heterogeneous, and Mo–MnO2 could repeatedly be reused while keeping its high catalytic performance. Besides sulfide oxygenation, Mo–MnO2 could efficiently catalyze several aerobic oxidative functional group transformations through single-electron transfer oxidation processes, namely, oxygenation of alkylarenes, oxidative α-cyanation of trialkylamines, and oxidative S-cyanation of benzenethiols.

Ionic Crystals [M3O(OOCC6H5)6(H2O)3]4[α-SiW12O40] (M = Cr, Fe) as Heterogeneous Catalysts for Pinacol Rearrangement

Complexation of trinuclear oxo-centered carboxylates with a silicododecatungstate resulted in the formation of ionic crystals of [M(3)O(OOCC(6)H(5))(6)(H(2)O)(3)](4)[α-SiW(12)O(40)]·nH(2)O·mCH(3)COCH(3) [M = Cr (Ia), Fe (IIa)]. Treatments of Ia and IIa at 373 K in vacuo formed guest-free phases Ib and IIb, respectively. Compounds Ib and IIb heterogeneously catalyzed the pinacol rearrangement to pinacolone with high conversion at 373 K, and the catalysis is suggested to proceed size selectively in the solid bulk.

Reduction‐Induced Highly Selective Uptake of Cesium Ions by an Ionic Crystal Based on Silicododecamolybdate

Cation adsorption and exchange has been an important topic in both basic and applied chemistry relevant to materials synthesis and chemical conversion, as well as purification and separation. Selective Cs(+) uptake from aqueous solutions is especially important because Cs(+) is expensive and is contained in radioactive wastes. However, the reported adsorbents incorporate Rb(+) as well as Cs(+) , and an adsorbent with high selectivity toward Cs(+) has not yet been reported. Highly selective uptake of Cs(+) by an ionic crystal (etpyH)2 [Cr3O(OOCH)6 (etpy)3]2 [α-SiMo12 O40 ]⋅3 H2O (etpy =4-ethylpyridine) is described. The compound incorporated up to 3.8 mol(Cs(+) ) mol(s)(-1) (where s=solid) by cation-exchange with etpyH(+) and reduction of silicododecamolybdate with ascorbic acid. The amount of Cs(+) uptake was comparable to that of Prussian blue, which is widely recognized as a good Cs(+) adsorbent. Moreover, other alkali-metal and alkaline-earth-metal cations were almost completely excluded (<0.2 mol mol(s)(-1)).

A New Rechargeable Sodium Battery Utilizing Reversible Topotactic Oxygen Extraction/Insertion of CaFeOz (2.5 ≤ z ≤ 3) in an Organic Electrolyte

At present, significant research efforts are being devoted both to identifying means of upgrading existing batteries, including lithium ion types, and also to developing alternate technologies, such as sodium ion, metal-air, and lithium-sulfur batteries. In addition, new battery systems incorporating novel electrode reactions are being identified. One such system utilizes the reaction of electrolyte ions with oxygen atoms reversibly extracted and reinserted topotactically from cathode materials. Batteries based on this system allow the use of various anode materials, such as lithium and sodium, without the requirement to develop new cathode intercalation materials. In the present study, this concept is employed and a new battery based on a CaFeO3 cathode with a sodium anode is demonstrated.

Composites of [γ-H2PV2W10O40]3− and [α-SiW12O40]4− supported on Fe2O3 as heterogeneous catalysts for selective oxidation with aqueous hydrogen peroxide

Composites of [γ-H2PV2W10O40]3− and [α-SiW12O40]4− supported on Fe2O3 (PV2-SiW12/Fe2O3, in particular, the molar ratio of PV2/SiW12 = 1/1) could act as effective and reusable heterogeneous catalysts for selective oxidation with aqueous hydrogen peroxide. In the presence of PV2-SiW12/Fe2O3, various kinds of organic substrates such as alkenes, sulfides, arenes, and alkanes could selectively be converted into the corresponding oxygenated products in moderate to high yields. The observed catalyses for the present oxidations were intrinsically heterogeneous, and PV2-SiW12/Fe2O3 could be reused at least three times for each oxidation (epoxidation, sulfoxidation, and arene hydroxylation) without appreciable losses of the high catalytic performance.