Water and catalytic isomerization of linear allylic alcohols by [RuCp(H₂O-κO)(PTA)₂]⁺(PTA = 1,3,5-triaza-7-phosphaadamantane)

Abstract

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.

Good isomerization of 2-cyclohexenol by two Ru(ii) complexes, synthesis and characterization of a reaction intermediate

“…8 The study of the isomerization of This behaviour can justify why water is needed in the medium but does not explain why in the series of allylic alcohols from 3-buten-2-ol to 1-octen-3-ol the conversion to ketone depends on the length of the tail of the alcohol and why 1-hexen-3-ol is the most reluctant to undergo isomerization. 16 The possible reason for this behaviour could come from the tail of the alcohol that sterically hinders the reaction, but this hypothesis needs to be supported by experimental and theoretical evidences. With this target in mind, the assessment of how 1 and 2 catalyze the isomerization of the secondary allylic alcohol 2-cyclohexenol, the cyclic analogue of the 1-hexen-3ol, can provide valuable information to solve this question.…”

Novel Ruthenium-Silver PTA-Based Polymers and Their Behavior in Water

“…Standard Schlenk-tube techniques with freshly distilled and oxygen-free solvents were employed. The hydrosoluble phosphine PTA and complex [RuClCp(PPh 3 ) 2 ] were prepared as reported in the literature [11,12].…”

Stereoisomeric Control in [RuCl2(PTA)2(2L)] Complexes (2L=2py or bpy): From Theoretical Calculations to a 2+2 Metallacycle of Pyridylporphyrins

“…PTA binds strongly to Ru(II), as well as to most transition metal ions, through the soft P atom (PTA‐κ P ), and it typically imparts excellent water solubility to its complexes by virtue of H‐bonding of H 2 O molecules to the tertiary amine nitrogens [2] . For this reason complexes with PTA (and modified PTA) ligands have been investigated as potential anticancer drugs, [2–18] and as homogeneous catalysts in aqueous solution or in biphasic aqueous‐organic conditions [2,19–35] …”