Ricerc@Sapienza

Biomimetic models of short-lived enzymatic reaction intermediates can give useful insight into the properties and coordination chemistry of transition metal complexes. In this work we investigate a high-valent iron(IV)-oxo porphyrin cation radical complex, namely [FeIV(O)(TPFPP+•)]+ where TPFPP is the dianion of 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin. The [FeIV(O)(TPFPP+•)]+ ion was studied by ion-molecule reactions in a Fourier transform-ion cyclotron resonance mass spectrometer through reactivities with 1,3,5-cycloheptatriene, 1,3-cyclohexadiene and toluene.

Cisplatin (cis-diamminedichloroplatinum(II), cis-[PtCl2(NH3)2]), widely used drug in cancer treatment,
has been allowed to react with simple molecular targets (L) mimicking biological functional groups.
The selected molecules (L = acetamide, dimethylacetamide, urea and thiourea) react by ligand exchange
leading to cis-[PtCl(NH3)2(L)]+ complexes that have been assayed by ESI-MS, IRMPD spectroscopy and

The study of Pt(IV) antitumor prodrugs able to circumvent some drawbacks of the conventional Pt(II) chemotherapeutics is the focus of a lot of attention. This paper reports a thorough study based on experimental methods (reduction kinetics, electrochemistry, tandem mass spectrometry and IR ion spectroscopy) and quantum–mechanical DFT calculations on the reduction mechanism of cisplatin-based Pt(IV) derivatives having two hydroxido (1), one hydroxido and one acetato (2), or two acetato ligands (3) in axial position.