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Mixed-Valent Cyanoplatinates Featuring Neptunyl-Neptunyl Cation-Cation Interactions
Philip A Smith1, Sarah M Hickam1, Jennifer E S Szymanowski1
1Department of Civil and Environmental Engineering and Earth Sciences , University of Notre Dame , Notre Dame , Indiana 46556 , United States.
Abstract:
The tetracyanoplatinate ligand was employed in synthesizing the first neptunyl cyanoplatinate complexes. Results indicate in situ oxidation of Pt(II) by Np(V/VI) to form mixed-valent Pt-Pt stacked columnar chains linked by cation-cation interaction induced chains of Np(V) polyhedra into a two-dimensional sheet structure. The Pt-Pt stacking distances of 3.04-3.05 Å are the longest reported columnar platinophilic interactions among mixed-valent tetracyanoplatinate structures. These complexes further illustrate the marked chemical differences and structural diversity of solid-state Np(V) coordination complexes with regard to Np(VI) and U(VI).
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