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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.

inorganic chemistry

LaSrCo0.5Rh0.5O3.25 and LaSrNi0.5Rh0.5O3.25:Topochemically Reduced, Mixed Valence Rh(I)/Rh(III) Oxides