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LaSrCo_{0.5}Rh_{0.5}O_{3.25} and LaSrNi_{0.5}Rh_{0.5}O_{3.25}:Topochemically Reduced, Mixed Valence Rh(I)/Rh(III) Oxides

Xu, Z; Palgrave, RG; Hayward, MA; (2020) LaSrCo_{0.5}Rh_{0.5}O_{3.25} and LaSrNi_{0.5}Rh_{0.5}O_{3.25}:Topochemically Reduced, Mixed Valence Rh(I)/Rh(III) Oxides. Inorganic Chemistry , 59 (18) pp. 13767-13773. 10.1021/acs.inorgchem.0c02131. Green open access

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Abstract

Topochemical reduction of the n = 1 Ruddlesden–Popper phases LaSrCo_{0.5}Rh_{0.5}O_{4} and LaSrNi_{0.5}Rh_{0.5}O_{4} with Zr yields LaSrCo_{0.5}Rh_{0.5}O_{3.25} and LaSrNi_{0.5}Rh_{0.5}O_{3.25}, respectively. Magnetization and XPS data reveal that while the rhodium centers in LaSrCo_{0.5}Rh_{0.5}O_{3.25} and LaSrNi_{0.5}Rh_{0.5}O_{3.25} have an average oxidation state of Rh^{2+}, these are actually mixed valence Rh(I,III) compounds, with the disproportionation of Rh^{2+} driven by the favorability of locating d^{8} Rh^{1+} and d^{6} Rh^{3+} cations within square-planar and square-based pyramidal coordination sites, respectively.

Type: Article
Title: LaSrCo_{0.5}Rh_{0.5}O_{3.25} and LaSrNi_{0.5}Rh_{0.5}O_{3.25}:Topochemically Reduced, Mixed Valence Rh(I)/Rh(III) Oxides
Location: United States
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acs.inorgchem.0c02131
Publisher version: https://doi.org/10.1021/acs.inorgchem.0c02131
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher's terms and conditions.
Keywords: Palladium, Oxides, Oxidation state, Transition metals, Cations
UCL classification: UCL
UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10110568
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