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Novel Syntheses of Mono‐ and Bisphosphonated Aromatic Phosphanes by Consecutive Pd‐Catalyzed P–C Coupling Reactions and Nucleophilic Phosphanylation – X‐ray Structure of Ph 2 P–C 6 H 4 – m ‐PO 3 Na 2 · 5.5 H 2 O · i PrOH
Author(s) -
Machnitzki Peter,
Nickel Thomas,
Stelzer Othmar,
Landgrafe Claudia
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199807)1998:7<1029::aid-ejic1029>3.0.co;2-7
Subject(s) - chemistry , catalysis , nucleophile , x ray , coupling (piping) , medicinal chemistry , palladium , stereochemistry , crystallography , organic chemistry , mechanical engineering , physics , quantum mechanics , engineering
The triphenylphosphane derivatives 2a and 5 , bearing one and two phosphonic ester groups, are accessible in high yields by consecutive Pd‐catalyzed P–C coupling reactions of p ‐bromoiodobenzene with Ph 2 PH and PhPH 2 , respectively, and then with diethyl phosphite. Ester hydrolysis yields the highly water‐soluble sodium salts of mono‐ and bis‐phosphonated triphenylphosphane, 3a and 6 , respectively. On reaction of the p ‐ and m ‐fluorophenylphosphonic diethyl esters 7a , 7b with Ph 2 PK and subsequent ester hydrolysis the isomeric disodium (diphenylphosphano)phenylphosphonates 3a , 3b were obtained. The X‐ray structure of Ph 2 P(C 6 H 4 – m ‐PO 3 Na 2 ) · 5.5 H 2 O · i PrOH (space group Cmc 2 1 ) has been determined. In the solid state, it forms a layer structure with hydrophilic (PO 3 2– , H 2 O, i PrOH) and hydrophobic (Ph 2 P) compartments, in which the PO 3 2– anionic groups are not engaged in coordination of the sodium cations.