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

Zoric, Marija R.; Singh, Varun; Zeller, Matthias; Glusac, Ksenija D.

doi:10.1002/poc.3975

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

Journal Article · Thu Jun 06 00:00:00 EDT 2019 · Journal of Physical Organic Chemistry

DOI:https://doi.org/10.1002/poc.3975· OSTI ID:1582574

Zoric, Marija R. ^[1]; Singh, Varun ^[1]; Zeller, Matthias ^[2]; Glusac, Ksenija D. ^[1]

Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Purdue Univ., West Lafayette, IN (United States)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); Youngstown State Univ., Youngstown, OH (United States); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1582574

Journal Information:: Journal of Physical Organic Chemistry, Vol. 32, Issue 10; ISSN 1099-1395

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
conformation
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CCDC 1566338: Experimental Crystal Structure Determination R., Zoric, Marija; Varun, Singh,; Matthias, Zeller, https://doi.org/10.5517/ccdc.csd.cc1pkx16 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1566339: Experimental Crystal Structure Determination R., Zoric, Marija; Varun, Singh,; Matthias, Zeller, https://doi.org/10.5517/ccdc.csd.cc1pkx27 The current record is supplemented by this dataset	dataset	January 2019

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

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