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Chirale Tripod‐Liganden mit Phosphit‐Donorgruppe: Synthese und Komplexchemie
Author(s) -
Scherer Johannes,
Huttner Gottfried,
Büchner Michael
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290617
Subject(s) - chemistry , tripod (photography) , stereochemistry , coordination complex , rhodium , ligand (biochemistry) , medicinal chemistry , nuclear magnetic resonance spectroscopy , phosphinite , cyclooctadiene , tripodal ligand , metal , crystal structure , crystallography , catalysis , organic chemistry , biochemistry , physics , receptor , optics
Chiral Tripodal Ligands Bearing a Phosphite Donor Group: Synthesis and Coordination Chemistry The mechanism of the reaction of epichlorohydrine (H–CH 2 Cl) ( 1 ) 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(CH 2 P(Ph) 2 )(CH 2 Cl) ( 2 ) and epoxides (Ph) 2 PCH 2 – ( 3 ) are characterized as intermediates. The mechanism leads to a rapid one‐pot method for the synthesis of chiral racemic as well as enantiomerically pure bis(phosphanyl) alcohols HOCH(CH 2 PR 2 )(CH 2 PR 2 ′ ) ( 4 ). The resulting bis(phosphanyl) alcohols 4 react easily with X 2 PCl (X = Cl; Ph; or X 2 = 1,2‐ethanedioxy‐2,2′‐biphenyldiyldioxy‐) to yield the mixed donor group tripodal ligands X 2 POCH(CH 2 PR 2 )(CH 2 PR′ 2 ) ( 5, 6 ) containing both phosphite, phosphinite or phosphorodichloridite and phosphane donor groups. The identity of these compounds were proved by 1 H‐, 31 P‐ and 13 C‐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]PF 6 } ( 7 ) of the ligand 5c , exhibiting the typical hetero‐bicyclooctane tripod metal cage of this type of tripod complexes.