Conformational and stereoelectronic investigation of chloromethyl methyl sulfide and its sulfinyl and sulfonyl analogs

dc.creatorDucati, LC
dc.creatorFreitas, MP
dc.creatorTormena, CF
dc.creatorRittner, R
dc.date2006
dc.dateDEC 4
dc.date2014-11-19T22:54:30Z
dc.date2015-11-26T18:06:45Z
dc.date2014-11-19T22:54:30Z
dc.date2015-11-26T18:06:45Z
dc.date.accessioned2018-03-29T00:48:55Z
dc.date.available2018-03-29T00:48:55Z
dc.identifierJournal Of Molecular Structure. Elsevier Science Bv, v. 800, n. 41699, n. 45, n. 50, 2006.
dc.identifier0022-2860
dc.identifierWOS:000242743600005
dc.identifier10.1016/j.molstruc.2006.03.085
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/56526
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/56526
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/56526
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1293431
dc.descriptionThe rotational equilibria of some sulfur-containing model compounds were theoretically determined, and a rationalization of the effects responsible for the results obtained is given. Experimental approaches, namely NMR and infrared, were also used to show the gauche (Cl-C-S-CH3 fragment) prevalence for these compounds and allowed us to elucidate the orbital interactions involved in such systems. The gauche rotamer of the sulfide is about 3.2 kcal mol(-1) more stable than anti in the gas phase. For the sulfinyl derivative the relative energies for the most stable rotamers are 0.0, 1.0 and 1.7 kcal mol(-1), corresponding to gauche-1 (C-Cl antiperiplanar to S=O), gauche-2 (C-Cl antiperiplanar to lone pair) and anti. The calculated energy difference (anti-gauche) between the sulfonyl rotamers is 2.6 kcal mol(-1). Natural bond orbital analysis indicated that the anomeric effect (n(S) -> sigma*(C-Cl)) plays the main role in stabilization of gauche in the sulfide compound, and that other important hyperconjugative interactions also occur for the remaining compounds. (c) 2006 Elsevier B.V. All rights reserved.
dc.description800
dc.description41699
dc.description45
dc.description50
dc.languageen
dc.publisherElsevier Science Bv
dc.publisherAmsterdam
dc.publisherHolanda
dc.relationJournal Of Molecular Structure
dc.relationJ. Mol. Struct.
dc.rightsfechado
dc.rightshttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy
dc.sourceWeb of Science
dc.subjectsulfur compounds
dc.subjecthyperconjugation
dc.subjectNBO
dc.subjectNMR
dc.subjectinfrared
dc.subjectR(0) Structural Parameters
dc.subjectInternal-rotation
dc.subjectBarriers
dc.subjectSpectra
dc.subjectDensity
dc.subjectEther
dc.titleConformational and stereoelectronic investigation of chloromethyl methyl sulfide and its sulfinyl and sulfonyl analogs
dc.typeArtículos de revistas


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