title: Hydride in BaTiO2.5H0.5: A Labile Ligand in Solid State Chemistry.
abstract: In synthesizing mixed anion oxides, direct syntheses have often been employed, usually involving high temperature and occasionally high pressure. Compared with these methods, here we show how the use of a titanium perovskite oxyhydride (BaTiO2.5H0.5) as a starting material enables new multistep low temperature topochemical routes to access mixed anion compounds. Similar to labile ligands in inorganic complexes, the lability of H(-) provides the necessary reactivity for syntheses, leading to reactions and products previously difficult to obtain. For example, BaTiO2.5N0.2 can be prepared with the otherwise inert N2 gas at 400-600 °C, in marked contrast with currently available oxynitride synthetic routes. F(-)/H(-) exchange can also be accomplished at 150 °C, yielding the oxyhydride-fluoride BaTi(O, H, F)3. For BaTiO2.4D0.3F0.3, we find evidence that further anionic exchange with OD(-) yields BaTiO2.4(D(-))0.26(OD(-))0.34, which implies stable coexistence of H(+) and H(-) at ambient conditions. Such an arrangement is thermodynamically unstable and would be difficult to realize otherwise. These results show that the labile nature of hydride imparts reactivity to oxide hosts, enabling it to participate in new multistep reactions and form new materials.
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University , Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Naoya
authors.initials: N
authors.lastname: Masuda
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University , Nishikyo-ku, Kyoto 615-8510, Japan.|PRESTO, Japan Science and Technology Agency (JST) , Kawaguchi-shi, Saitama 332-0012, Japan.
authors.forename: Yoji
authors.initials: Y
authors.lastname: Kobayashi
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Université de Rennes 1 , Bâtiment 10B, Campus de Beaulieu, Rennes F-35042, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Hernandez
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Université de Rennes 1 , Bâtiment 10B, Campus de Beaulieu, Rennes F-35042, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Bataille
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR CNRS 6226, Université de Rennes 1 , Bâtiment 10B, Campus de Beaulieu, Rennes F-35042, France.
authors.forename: Serge
authors.initials: S
authors.lastname: Paofai
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University , Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Hajime
authors.initials: H
authors.lastname: Suzuki
authors.affiliation: Institut Laue-Langevin , 6, rue Jules Horowitz, Grenoble 38000, France.
authors.forename: Clemens
authors.initials: C
authors.lastname: Ritter
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.
authors.forename: Naoki
authors.initials: N
authors.lastname: Ichijo
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.
authors.forename: Yasuto
authors.initials: Y
authors.lastname: Noda
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.
authors.forename: Kiyonori
authors.initials: K
authors.lastname: Takegoshi
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University , Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Cédric
authors.initials: C
authors.lastname: Tassel
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University , Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Takafumi
authors.initials: T
authors.lastname: Yamamoto
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University , Nishikyo-ku, Kyoto 615-8510, Japan.|CREST, Japan Science and Technology Agency (JST) , Kawaguchi-shi, Saitama 332-0012, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Kageyama