Plane hydrolysis of coordinated phosphorus and phosphorus sulphide

INOR 783

Maurizio Peruzzini, mperuzzini@iccom.cnr.it1, Massimo Di Vaira2, Stefano Seniori Costantini2, and Piero Stoppioni2. (1) ICCOM CNR, Via Madonna del Piano, 10, 50019 Sesto Fiorentino FI, Italy, (2) Department of Chemistry, University of Florence, Via della Lastruccia, Sesto Fiorentino, Italy
Once coordinated to a transition metal-ligand fragment, white phosphorus exhibits distinctive reactivity patterns quite different from those shown by the free molecule.[1] A similar behaviour is also shown by related molecules, such as P4S3, tetraphosphorus trisulphide, which shares with P4 the same tetrahedral-tetraphosphorus topology. In this communication, we report on the astonishing hydrolysis undergone by ruthenium complexes bearing white phosphorus[2] or tetraphosphorus trisulphide[3] coordinated either as η1- or μ,η1,1-ligand to the C5R5RuL2 fragment (R = H, Me; L = tertiary phosphine). Among the hydrolysis products are worth mentioning the highly stable cations Cp*RuL2(PH3) and Cp*RuL2(PH2SH) which contains the unusual phosphine, PH3, and the unprecedented thiophosphinous acid, PH2SH, ligands. All of these complexes have been characterised in solution by multinuclear NMR spectroscopy and, in the solid state, by X-ray crystallography.

References: [1] Peruzzini, M.; Gonsalvi, L.; Romerosa, A. Chem. Soc. Rev. 2005, 34, 1038. [2] Di Vaira, M.; Frediani, P.; Seniori Costantini, S.; Peruzzini, M.; Stoppioni, P. Dalton Trans. 2005, 4330. [3] Di Vaira, M.; Seniori Costantini, S.; Peruzzini, M.; Stoppioni, P. Chem. Eur. J. 2007, in press.

 

Main Group Chemistry
9:00 AM-12:20 PM, Wednesday, August 22, 2007 BCEC -- 205C, Oral

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007