Inverted Carbon Geometries: Challenges to Experiment and Theory

Autor:	Harald Untenecker, Peter R. Schreiner, Matthias Bremer, Andrey A. Fokin, Pavel A. Gunchenko
Rok vydání:	2015
Předmět:	Hexane Pentane chemistry.chemical_compound Electron density Bicyclic molecule Chemistry Cubane Computational chemistry Organic Chemistry Ab initio Molecule Large deviations theory
Zdroj:	The Journal of Organic Chemistry. 80:6520-6524
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.5b00845
Popis:	Disproving a long C-C-bond textbook example: The reported 1.643 Å C-C bond in 5-cyano-1,3-dehydroadamantane was redetermined and "only" amounts to 1.584 Å. While this value is well reproduced with ab initio methods, some common DFT approaches perform poorly and are only consistent with CCSD(T)/cc-pVTZ optimizations for noninverted carbons. Large deviations from experiment were also found for other molecules with atypical electron density distributions, e.g., cubane, bicyclo[2.2.0]hexane, and bicyclo[2.1.0]- and bicyclo[1.1.1]pentane, thereby presenting challenging structures for some DFT implementations.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::eb925d0d2b7c8854a181ab0791f03e7b https://doi.org/10.1021/acs.joc.5b00845 Zobrazit plný text záznamu