A computational mechanistic investigation into the reduction of Pt(IV) prodrugs with two axial chlorides by biological reductants

It is widely reported that the Pt(iv) prodrugs with two axial chlorido ligands are reduced by biological reductants via a chloride-bridged inner-sphere mechanism. By contrast, in this contribution, we demonstrate that although this approach might be true for the reductants with sulphur donors, the reduction by ascorbates preferentially occurs via an outer sphere mechanism.