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Updated: Jun 14, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Two hexa-TM-containing (TM = Co2+ and Ni2+) {P2W12}-based trimeric tungstophosphates
Shuang Yao1, Zhiming Zhang, Yangguang Li
1Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Renmin Street No. 5268, Changchun, Jinlin 130024, P. R. China.
Abstract:
Reactions of hexavacant polyoxotungstates [H(2)P(2)W(12)O(48)](12-) ({P(2)W(12)}) with transition-metal (TM), and alkali-metal ions lead to the isolation of two hexa-TM-containing polyoxotungstates Na(15)[Na(3) subset {M(H(2)O)(4)}(6){WO(H(2)O)}(3)(P(2)W(12)O(48))(3)].xH(2)O (M = Co(2+), x = 109 for 1; M = Ni(2+), x = 110 for 2). Single-crystal X-ray diffraction analysis revealed that compounds 1 and 2 both crystallized in the orthorhombic system, space group Cmcm, with lattice constants a = 21.353(3) A, b = 32.114(3) A, c = 33.848(4) A, for 1; a = 21.643(6) A, b = 31.870(6) A, c = 33.861(7) A for 2. Polyoxoanions [Na(3) subset {M(H(2)O)(4)}(6){WO(H(2)O)}(3)(P(2)W(12)O(48))(3)](15-) in 1 and 2 exhibit a crown-type structure composed of a [{WO(H(2)O)}(3)(P(2)W(12)O(48))(3)](18-) (abbreviated as {P(6)W(39)}) shell encapsulating six TM ions and three Na(+) cations. Polyoxoanions 1 and 2 represent the first hexa-TM-containing {P(2)W(12)}-based trimeric POMs, which offer new examples with the potentially aqua-ligand-induced capability of "trapping" metal ions in the {P(6)W(39)} shell. Electrocatalytic studies show that compounds 1 and 2 display electrocatalytic activity to reduce nitrite.
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