Two novel trivacant Keggin-type polytungstates supported manganese carbonyl derivatives synthesized by degradation of metastable [γ-XW _(10)O _(36)] ~(8-) (X = Ge ~(IV), Si ~(IV))

摘要

Two novel trivacant Keggin-type polyoxometallate-based manganese carbonyl derivatives K _8[(OC) _3Mn(A-α-H _2GeW _9O _(34))]·10H _2O (1) and K _8[(OC) _3Mn(A-α-H _2SiW _9O _(34))]·11H _2O (2) have been synthesized by degradation of the metastable [γ-XW _(10)O _(36)] ~(8-) (X = Ge ~(IV), Si ~(IV)) in CH _3CN-H _2O solvent (1:2, vol.) and structurally characterized by elemental analyses, IR spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction analyses indicate that 1 and 2 are isomorphic and consist of a [(OC) _3Mn] ~+ group and a trivacant [A-α-H _2XW _9O _(34)] ~(8-) fragment, which exhibit the first examples of trivacant Keggin-type metal carbonyl derivatives. Additionally, the electrocatalytic properties of both for NO _2 - oxidation have been investigated.