A class of so-called POP ligands (Xanthos, NiXantphos, DPEphos) are of a great interest to the coordination chemistry due to their wide P-M-P bite angles and ability to show either κ2- or κ3-binding modes. Such κ2–κ3-rearrangement is valuable for catalytic application and internal stabilization of intermediates. To widen the scope of ruthenium-based catalysts for Atom Transfer Radical Polymerization (ATRP) two new approaches to the synthesis of closo-ruthenacarboranes with aforementioned POP ligands were developed and six new 17-e (3,3-(POP)-3-Cl-closo-3,1,2-RuC2B9H11; 2, 4, 7) and 18-e (3,3-(POP)-3-NCCH3-closo-3,1,2-RuC2B9H11; 3, 5, 8) clusters were synthesized and characterized by means of NMR or ESR spectroscopy, MALDI mass-spectrometry and single crystal X-ray diffraction studies. The unique 18-e complex of Ru(II) with dioxygen ligand 3,3-(DPEphos)-3-(η2-O2)-closo-3,1,2-RuC2B9H11 (9) was isolated and characterized by X-ray diffraction. It was shown that aforementioned POP ligands coordinate to ruthenium by two phosphorus atoms in a κ2-fashion. The performed electrochemical studies have shown reversible Ru(II)-Ru(III) transition making the complexes suitable for application in catalysis of polymerization. The test experiments on methyl methacrylate (MMA) polymerization indicate the proceeding of the process in according with an ATRP mechanism.