Influence of the chloride counterion on the redox reactivity of tetraammineplatinum(II) cation with octacyanotungstate(V) anion

Add time:08/07/2019    Source:sciencedirect.com

The redox reaction between [Pt(NH3)4]2+ and [W(CN)8]3− in the presence of Cl− anions in aqueous solution affords single crystals of [PtII(NH3)4]2[WIV(CN)8] and [PtIV(NH3)4Cl2]Cl2. Trapped cyano ligands of [W(CN)8]4− rectangular antiprisms of D2 point symmetry between parallel Pt(II) square planes show that the inner-sphere redox pathway is prohibited. The presence of Cl− counterions enables the formation of [Pt(NH3)4Cl2]Cl2 as the product of the rare outer-sphere pathway of the oxidation of Pt(II) by [W(CN)8]3−.

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