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Updated: Jun 5, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Directing the Linkage of Small Polyoxometalate Building Blocks Using (Benzene)ruthenium Cations
Sugiarto1, Yuudai Iwai2, Ryo Ohtani2
1Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527, Japan.
Abstract:
Oligomerization of monomeric molybdate and tungstate oxyanions in the presence of organometallic cations produces a group of organometallic-polyoxometalate clusters, which have diverse structures based on cubane-like {M4O4} units resembling the structure of oxide surfaces. This work investigated the oligomerization of [MoO4]2- and [WO4]2- oxyanions in aqueous solutions in the presence of {Ru(C6H6)}2+ as the organometallic structure-directing agents. The reactions produced a mixture of several species, and fractional crystallization by adjusting crystallization temperature and molar ratios of Ru:Mo or Ru:W allowed the isolation of seven types of (benzene)ruthenium-polyoxometalate complexes: [{Ru(C6H6)}4Mo4O16] (1), [{Ru(C6H6)(OH)}3HMoO4][MoO4] (2), [{Ru(C6H6)}4H2Mo5O20] (3), [{Ru(C6H6)}4W2O10] (4), Na6[{Ru(C6H6)}2H2W8O30] (5), [{Ru(C6H6)}5H2W6O24] (6), and [{Ru(C6H6)(OH)}6W2O7][{Ru(C6H6)}2{Ru(C6H6)(OH2)}2H2W8O30]2 (7). They comprise small, reactive iso-polyoxometalate building blocks that are capped by {Ru(C6H6)}2+ cations, resulting in cubane-like {Ru3MO4}, {Ru2M2O4}, or {RuM3O4} (M = Mo or W) structural motifs. Moreover, the molecular crystal of 1 contains extensive C-H···O hydrogen bonds, and it undergoes a reversible crystal-to-amorphous-to-crystal transition upon dehydration-hydration cycles.
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