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

Abstract

The 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:
 [1];  [1];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Youngstown State Univ., Youngstown, OH (United States); USDOE
OSTI Identifier:
1582574
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Organic Chemistry
Additional Journal Information:
Journal Volume: 32; Journal Issue: 10; Journal ID: ISSN 1099-1395
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 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.
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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. https://doi.org/10.1002/poc.3975
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Zoric, Marija R., Singh, Varun, Zeller, Matthias, and Glusac, Ksenija D. Thu . "Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups". United States. https://doi.org/10.1002/poc.3975. https://www.osti.gov/servlets/purl/1582574.
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@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 = {The 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 = {Thu Jun 06 00:00:00 EDT 2019},
month = {Thu Jun 06 00:00:00 EDT 2019}
}
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https://doi.org/10.1002/poc.3975
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