A new water soluble complex [RuCp(HO-κO)(PTA)] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane) has been synthesized and fully characterized by NMR and IR. The crystal structure of 1(CFSO)·3.5HO was characterized by single crystal X-ray determination. The catalytic activity of this complex was evaluated for the isomerisation of linear allylic alcohols from 3-buten-2-ol to 1-octen-3-ol into the correspondent ketones under both an inert atmosphere and in air, using as solvents: water, the substrate, mixtures of water/substrate, MeOH and mixtures of MeOH/water. An isomerization experiment on a mixture of all the studied allylic alcohols was also carried out.

The complex [RuCp(PPh3)2(HdmoPTA)](OSO2CF3)2 (2; HdmoPTA = 3,7-H-3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) was synthesized and characterized. Its crystal structure was determined by single-crystal X-ray diffraction. The complex showed a more potent antiproliferative activity than cisplatin against a representative panel of human cancer cells.

We describe the intermediate of the reaction between a ruthenium complex and the 1-propen-3-ol in water by an atomistic approach for gaining information about the conformation and dynamics of complex molecules in aqueous solution, which combines DFT based ab initio molecular dynamics (AIMD) and neutron scattering data based on Empirical Potential Structure Refinement (EPSR) simulations. We apply our method to the study of the water soluble h 2-allylic complex [RuCp(exo-h 2-CH2=CH-CH2-OH)(PTA)2] + (2) (PTA = 1,3,5-triaza-7-phosphaadamantane), a significant intermediate in the isomerisation of 1-propen-3-ol into propanal catalysed by {RuCp(H2O-κO)(PTA)2} +. We identify the factors responsible for the stabilisation of a specific conformer of 2 in water solution and, for the first time, we demonstrate the direct involvement of water molecules in the formation of this species. In particular, we show that long-lived (ca. 10 ps) bonded chains of water molecules play a crucial role in influencing the conformation and, potentially, the chemical reactivity of 2.

The catalytic activities of [RuClCp(PTA)2] (1) and [RuCp(PTA)2(H2O-κO)]OTf (2) were assessed for the redox isomerization of the cyclic allylic alcohol 2-cyclohexenol into cyclohexanone in water and biphasic media. Complex 2 showed unprecedented good TONs for the studied conversion both in water (TON = 647) and in the biphase of cyclohexene/H2O (TON = 3420) while 1 showed a lower but also good activity (water TON = 95, biphasic TON = 100). The catalytic reaction intermediate [RuCp(PTA)2(η2-C6H9OH)]CF3SO3 (3) was synthesized and characterized using NMR.

Synthesis, characterization and the antiproliferative activity of a new bimetallic complex [RuCp(PPh)-μ-dmoPTA-1κP:2kN,N'-CoCl]OTf·0.25HO are described. The stability of the complex was studied under air and N atmospheres and in CDCl, DMSO, water and the cell culture medium, at room temperature and 40 °C. The complex showed an enhanced antiproliferative activity (up to six-fold) when compared with its parent complex [RuCp(PPh)(HdmoPTA)] against human lung, cervix, breast, and colon solid tumor cell lines.