Unprecedented Stereospecific Ligand Exchange at a W ≡ W Template

Steven D. Dietz; Nancy W. Eilerts; Joseph A. Heppert

doi:10.1002/anie.199200661

Unprecedented Stereospecific Ligand Exchange at a W ≡ W Template

Steven D. Dietz, Nancy W. Eilerts, Joseph A. Heppert

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Abstract

Diastereomeric binaphtholato complexes with the composition [W₂(bino)₂(OtBu)₂] (H₂bino = 1,1′‐bi‐2‐naphthol), the anti and gauche isomers 1 and 2, are formed from the reaction of [W₂(OtBu)₆] with rac H₂bino or (R)‐H₂bino 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 [W₂{(R,R,R)‐bino}₃]. The gauche arrangement of the tBuO ligands in 2 is apparently more favorable for intramolecular proton transfer. (Figure Presented.)

Original language	English
Pages (from-to)	66-68
Number of pages	3
Journal	Angewandte Chemie International Edition in English
Volume	31
Issue number	1
DOIs	https://doi.org/10.1002/anie.199200661
State	Published - Jan 1992

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@article{b77125c3298c468b9d732a4882cd1f6a,

title = "Unprecedented Stereospecific Ligand Exchange at a W ≡ W Template",

abstract = "Diastereomeric binaphtholato complexes with the composition [W2(bino)2(OtBu)2] (H2bino = 1,1′‐bi‐2‐naphthol), the anti and gauche isomers 1 and 2, are formed from the reaction of [W2(OtBu)6] with rac H2bino or (R)‐H2bino 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 [W2{(R,R,R)‐bino}3]. The gauche arrangement of the tBuO ligands in 2 is apparently more favorable for intramolecular proton transfer. (Figure Presented.)",

author = "Dietz, {Steven D.} and Eilerts, {Nancy W.} and Heppert, {Joseph A.}",

year = "1992",

month = jan,

doi = "10.1002/anie.199200661",

language = "English",

volume = "31",

pages = "66--68",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

number = "1",

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TY - JOUR

T1 - Unprecedented Stereospecific Ligand Exchange at a W ≡ W Template

AU - Dietz, Steven D.

AU - Eilerts, Nancy W.

AU - Heppert, Joseph A.

PY - 1992/1

Y1 - 1992/1

N2 - Diastereomeric binaphtholato complexes with the composition [W2(bino)2(OtBu)2] (H2bino = 1,1′‐bi‐2‐naphthol), the anti and gauche isomers 1 and 2, are formed from the reaction of [W2(OtBu)6] with rac H2bino or (R)‐H2bino 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 [W2{(R,R,R)‐bino}3]. The gauche arrangement of the tBuO ligands in 2 is apparently more favorable for intramolecular proton transfer. (Figure Presented.)

AB - Diastereomeric binaphtholato complexes with the composition [W2(bino)2(OtBu)2] (H2bino = 1,1′‐bi‐2‐naphthol), the anti and gauche isomers 1 and 2, are formed from the reaction of [W2(OtBu)6] with rac H2bino or (R)‐H2bino 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 [W2{(R,R,R)‐bino}3]. The gauche arrangement of the tBuO ligands in 2 is apparently more favorable for intramolecular proton transfer. (Figure Presented.)

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U2 - 10.1002/anie.199200661

DO - 10.1002/anie.199200661

M3 - Article

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