178674-44-7Relevant articles and documents
Chiral Tripodal Ligands Bearing a Phosphite Donor Group: Synthesis and Coordination Chemistry
Scherer, Johannes,Huttner, Gottfried,Buechner, Michael
, p. 697 - 713 (2007/10/03)
The mechanism of the reaction of epichlorohydrine (O-CH2-CH-CH2Cl) (I) with lithium phosphides is analysed. A neighbouring-group mechanism has been found to be the essential driving force in this reaction, Monophosphanyl alcohols such as HOCH(CH2P(Ph)2)(CH2Cl) (2) and epoxides (Ph)2PCH2-CH-CH2-O (3) are characterized as intermediates. The mechanism leads to a rapid one-pot method for the synthesis of chiral racemic as well as enantiomencally pure bis(phosphanyl) alcohols HOCH(CH2PR2){CH2PR2) (4). The resulting bis(phosphanyl) alcohols 4 react easily with X2PCl (X= Cl; Ph; or X2= 1,2-ethanedioxy-i 2,2′-biphenyldiyldi-oxy-) to yield the mixed donor group tripodal ligands X2POCH(CH2PR2)(CH2PR2) (5, 8) containing both phosphite, phosphinite or phosphorodichloridite and phosphane donor groups. The identity of these compounds were proved by 'H-, 31P- and 13C-NMR spectroscopy, mass spectra, microanalysis as well as X-ray analysis. The coordination capabilities of these novel ligands are demonstrated by the synthesis and characterization of a (cyclooctadiene)rhodium complex {[(5c)Rh(I)COD]PF6) (7) of the ligand 5c, exhibiting the typical hetero-bicyclooctane tripod metal cage of this type of tripod complexes. VCH Verlagsgesellschaft mbH, 1996.
