WATER-SOLUBLE PHOSPHANES - 10 - NOVEL SYNTHESES OF MONOPHOSPHONATED AND BISPHOSPHONATED AROMATIC PHOSPHANES BY CONSECUTIVE PD-CATALYZED P-CCOUPLING REACTIONS AND NUCLEOPHILIC PHOSPHANYLATION - X-RAY STRUCTUREOF PH2P-C6H4-M-PO3NA2.5.5H(2)O.IPROH

The triphenylphosphane derivatives 2a and 5, bearing one and two phosp honic ester groups, are accessible in high yields by consecutive Pd-ca talyzed P-C coupling reactions of p-bromoiodobenzene with Ph2PH and Ph PH2, respectively, and then with diethyl phosphite, Eater hydrolysis y ields the highly water-soluble sodium salts of mono- and bis-phosphona ted triphenylphosphane, 3a and 6, respectively. On reaction of the p- and m-fluorophenylphosphonic diethyl esters 7a, 7b with Ph2PK and subs equent ester hydrolysis the isomeric disodium (diphenylphosphano)pheny lphosphonates 3a, 3b were obtained. The X-ray structure of Ph2P(C6H4-m -PO3Na2) . 5.5 H2O . fPrOH (space group Cmc2(1)) has been determined. In the solid state, it forms a layer structure with hydrophilic (PO32- , H2O, fPrOH) and hydrophobic (Ph2P) compartments, in which the PO32- anionic groups are not engaged in coordination of the sodium cations.