Experimental Evidence of Phosphine Oxide Generation in Solution and Trapping by Ruthenium Complexes

Abstract

Dr. Schipper gave an important contribution to this article in terms of crucial discussion and interpretation of the preliminary electrochemical results and provided several important suggestions on how to characterize the otherwise elusive target compound.

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

“…Lately, these organophosphorus derivatives have drawn much attention. Tautomerization of SPOs to tricoordinated trivalent (    ) phosphinous acids (PAs, R 1 R 2 P−OH) in the presence of a transition metal complex [ML n ] allows the SPOs to act as P(III)−phosphane-like preligands (Scheme 13) [78,79]. The coordinated P(III)−phosphinous acid ligands stemming from SPOs are more than "classical" phosphanes and possess their own steric and electronic properties.…”

Electrochemical generation of P4 2– dianion from white phosphorus

“…The 31 P NMR spectral characteristics of the phosphorus products obtained correspond to those published earlier. 15 …”

“…14 Moreover, under the conditions of undivided electrolysis with a zinc anode, we succeeded in generation and stabili zation of a novel phosphorus compound, viz., phosphane oxide H 3 PO (see Ref. 15), which was considered previ ously as unstable.…”

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

“…The choice of solvent is relevant for the final result. Using MeOH and adding a 100-fold excess of water with respect to 2, the main products of hydrolysis are the oxyacids H 3 PO 3 (31%), H 3 PO 4 (31%) and the phosphine complex [CpRu(TPPMS) 2 (PH 3 )]PF 6 (3) (24%), the latter identified by independent synthesis [9]. The dimethyl phosphite ester, OP(H)(OCH 3 ) 2 (14%), likely obtained by reaction of the formed acid with the solvent, was also present and was identified by 31 P NMR [10].…”

“…In addition, the cage has the advantage to release P 4 at will. On the other hand, water-soluble ruthenium complexes such as 1 have been already successfully used to trap highly unstable phosphorus species such as phosphine oxide, H 3 PO, generated by electrochemical activation of white phosphorus carried out in water/ ethanol mixture [9].…”