Hydridotris(pyrazolyl)borate (Tp) ruthenium (II) complexes containing new phosphane ligands are described. The new complexes were obtained by electrophilic attack to a coordinated 1,3,5-triaza-7-phosphatricyclo[3.3.1.1(3,7)]decane (PTA) ligand. Thus, cationic complexes [RuX{kappa(3)(NNM-Tp}(PPh3)(1-R-PTA)][Y] (X = Cl, R = H (1), CH2Ph (4), CH2CH=CH2 (6), CH2C CH (8); X = 1, R = CH2Ph (5), CH2CH=CH2 (7)) and neutral [RuCl{kappa(3)(N,N,N)-Tp}(PPh3)(1-I-2-PTA)] (3) have been synthesized and characterized. For complexes [Ru{kappa(3)(N,N,N)-Tp}(PPh3)1-R-PTA)][Y] (R = CH2Ph, CH2CH=CH2) an unprecedented formal C-H activation has been observed in alcohols leading to complexes with 1-methyl-4-phenyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1(3,7)]decane , 4-(2-methoxyethyl)-1-methyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1 3,7]decane and 1-methyl-4-[2-(propan-2-yloxi)ethyl]-3,5-diaza-l-azonia7-phosphatricyclo [3,3.1.1(3,7)]decane ligands, respectively, and the mechanism explored through deuteriation experiments. The first I-2-charge transfer compound between 12 and a nitrogen which belongs to a ligand coordinated to a transition metal, (RuI(kappa(3)(NNM-Tp)(PPh3)(1-I-2-PTA)] is described.