The first water-soluble tetraphosphorus ruthenium complex. Synthesis, characterization and kinetic study of its hydrolysis

Reaction of the water-soluble complex [CpRu(TPPMS)2Cl] (1) [TPPMS = sodium salt of m-monosulfonated triphenylphosphine, Ph2P(m-C6H4SO3Na)] with 1 equiv of white phosphorus in the presence of TlPF6 or AgBF4 as chloride scavengers, yielded the stable hydrosoluble complexes [CpRu(TPPMS)2(η1-P4)]X (2) (X = PF6, BF4). Addition of water to DMF solutions of 2 causes hydrolysis ovf coordinated P4 giving as main products complexes [CpRu(TPPMS)2(PH3)]X (3) (X = PF6, BF4) together with hydrogen and phosphorous acid, H3PO3. The new complexes have been characterized by 1H and 31P NMR spectroscopy in solution. Kinetic data and activation parameters of the hydrolysis process are reported.

The new complex [CpRu(TPPMS)2(η1-P4)]+ has been isolated, representing the first example of stable water-soluble Ru complex bearing an η1-coordinated tetrahedro-P4 as ligand. Reaction with an excess of water yields [CpRu(TPPMS)2(PH3)]+ and H3PO3. A kinetic investigation on the hydrolysis reaction has been carried out in the temperature range 9–35 °C.Figure optionsDownload as PowerPoint slideHighlights
► The first water-soluble ruthenium complex bearing η1-P4 tetrahedron was isolated.
► Reaction with an excess of water yields [CpRu(TPPMS)2(PH3)]+ and H3PO3.
► The first kinetic study on the hydrolysis of η1-P4 moiety has been carried out.
► The activation parameters of the hydrolysis reaction have been obtained.