Structures and Rotational Barriers of a Diiodobinorsnoutane: Energetic Preference for Gauche Conformation

The diiodobinorsnoutane, bi­(5-iodopentacyclo­[4.3.0.02,4.03,8.05,7]­non-4-yl) (5), exists in a sterically hindered gauche conformation rather than an anti or an averaged (freely rotating) C 2v structure. Density functional theory (DFT) predictions place the gauche conformation 11 kcal/mol more stab...

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Published inJournal of organic chemistry Vol. 81; no. 15; pp. 6862 - 6866
Main Authors Herres, Joseph P., Moran, Caitlin A., Forman, Mark A., Hall, James E., McCauley, John P., Pivonka, Don E., Wesolowski, Steven S.
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 05.08.2016
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Summary:The diiodobinorsnoutane, bi­(5-iodopentacyclo­[4.3.0.02,4.03,8.05,7]­non-4-yl) (5), exists in a sterically hindered gauche conformation rather than an anti or an averaged (freely rotating) C 2v structure. Density functional theory (DFT) predictions place the gauche conformation 11 kcal/mol more stable than the anti conformation with a barrier of 17 kcal/mol connecting the minima. These are consistent with variable-temperature NMR (17.1 ± 0.8 kcal/mol) estimates and X-ray analysis. Predictions of the torsional profiles of the yet-unsynthesized bromo-, chloro-, and fluoro- analogues show a progressive lowering of the barriers.
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ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.6b01204