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Unprecedented Stereospecific Ligand Exchange at a W ≡ W Template
Author(s) -
Dietz Steven D.,
Eilerts Nancy W.,
Heppert Joseph A.
Publication year - 1992
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199200661
Subject(s) - stereospecificity , diastereomer , intramolecular force , chemistry , ligand (biochemistry) , proton , stereochemistry , medicinal chemistry , crystallography , catalysis , organic chemistry , physics , receptor , biochemistry , quantum mechanics
Diastereomeric binaphtholato complexes with the composition [W 2 (bino) 2 (O t Bu) 2 ] (H 2 bino = 1,1′‐bi‐2‐naphthol), the anti and gauche isomers 1 and 2 , are formed from the reaction of [W 2 (O t Bu) 6 ] with rac H 2 bino or ( R )‐H 2 bino respectively. Isomers 1 and 2 differ considerably in their thermodynamic stability: 1 is stable at room temperature and can be used for further diastereoselective exchange reactions, 2 decomposes in only a short time producing ter ‐butanol, isobutene, and [W 2 {( R,R,R )‐bino} 3 ]. The gauche arrangement of the t BuO ligands in 2 is apparently more favorable for intramolecular proton transfer.
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