Oxidation of Pt(II) to Pt(IV) complex with hydrogen peroxide in glycols

The reaction of cis, cis-[PtII(9-fm)(dmpda)] (9-fm=9-fluorenylidenemalonate, dmpda=2,2-dimethyl-1,3-propanediamine) with hydrogen peroxide in ethyleneglycol produces cis,trans,cis-[PtIV(9-fm)(OCH2CH2OH)(OH)(dmpda)]. Its crystal structure shows that the local geometry around the platinum atom approximates a typical octahedral arrangement with the added OCH2CH2OH/OH ligands in trans coordination sites. The molecules are packed in a two-dimensional assembly via van der Waals interactions, where the hydrophobic fluorenyl groups are arranged on both faces of the assembly plate whereas the hydrophilic groups fill up the inner part of the plate. The compound bearing both “inorganic OH” and “organic OH” is a potential precursor for further various functionalizations.