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:
-
- Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Purdue Univ., West Lafayette, IN (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (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.
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
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.
@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 = {2019},
month = {6}
}
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