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Title: Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups

Abstract

Conformational flexibility of three covalently linked alcohol dimers, composed of xanthenol units and diphenyl ether (DPE(OH)(2)), 9,9-dimethylxanthene (XAN(OH)(2)), or biphenyl (BP(OH)(2)) linkers was studied. The relative orientation of the two alcohol units (In-In, In-Out, and Out-Out conformers) in the model compounds was investigated using NMR spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Diols containing rigid linkers, such as XAN(OH)(2) and BP(OH)(2), favor the formation of an In-In conformer in solution, and the interconversion between different conformers was slow on the NMR timescale. Interestingly, XAN(OH)(2) adopted an In-Out conformation in the crystalline solid state, possibly due to additional intermolecular interactions. More flexible DPE(OH)(2) was found to freely interconvert on the NMR timescale. This study provides important structural information that can be utilized in catalysis, metal-ligation, and other applications.

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Youngstown State University
OSTI Identifier:
1582574
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Physical Organic Chemistry
Additional Journal Information:
Journal Volume: 32; Journal Issue: 10
Country of Publication:
United States
Language:
English
Subject:
conformation; conformational analysis; covalently linked dimers; dimer; interconversion

Citation Formats

Zoric, Marija R., Singh, Varun, Zeller, Matthias, and Glusac, Ksenija D. Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups. United States: N. p., 2019. Web. doi:10.1002/poc.3975.
Zoric, Marija R., Singh, Varun, Zeller, Matthias, & Glusac, Ksenija D. Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups. United States. doi:10.1002/poc.3975.
Zoric, Marija R., Singh, Varun, Zeller, Matthias, and Glusac, Ksenija D. Tue . "Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups". United States. doi:10.1002/poc.3975.
@article{osti_1582574,
title = {Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups},
author = {Zoric, Marija R. and Singh, Varun and Zeller, Matthias and Glusac, Ksenija D.},
abstractNote = {Conformational flexibility of three covalently linked alcohol dimers, composed of xanthenol units and diphenyl ether (DPE(OH)(2)), 9,9-dimethylxanthene (XAN(OH)(2)), or biphenyl (BP(OH)(2)) linkers was studied. The relative orientation of the two alcohol units (In-In, In-Out, and Out-Out conformers) in the model compounds was investigated using NMR spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Diols containing rigid linkers, such as XAN(OH)(2) and BP(OH)(2), favor the formation of an In-In conformer in solution, and the interconversion between different conformers was slow on the NMR timescale. Interestingly, XAN(OH)(2) adopted an In-Out conformation in the crystalline solid state, possibly due to additional intermolecular interactions. More flexible DPE(OH)(2) was found to freely interconvert on the NMR timescale. This study provides important structural information that can be utilized in catalysis, metal-ligation, and other applications.},
doi = {10.1002/poc.3975},
journal = {Journal of Physical Organic Chemistry},
number = 10,
volume = 32,
place = {United States},
year = {2019},
month = {10}
}

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