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dc.contributor.authorVassilikogiannakis, G.en
dc.contributor.authorChronakis, Nikosen
dc.contributor.authorOrfanopoulos, Michaelen
dc.creatorVassilikogiannakis, G.en
dc.creatorChronakis, Nikosen
dc.creatorOrfanopoulos, Michaelen
dc.date.accessioned2019-11-21T06:23:30Z
dc.date.available2019-11-21T06:23:30Z
dc.date.issued1998
dc.identifier.urihttp://gnosis.library.ucy.ac.cy/handle/7/56278
dc.description.abstractThe stereochemistry and secondary isotope effects of the [2 + 2] photocycloaddition of trans,trans- (7), cis,cis- (8), and cis,trans-2,4- hexadiene (9), 2,5-dimethyl-2,4-hexadiene (1), and its deuterated analogues 1-d1, 1-d6, and trans-1-d3 to C60 have been investigated. A loss of stereochemistry in the cyclobutane ring for photocycloaddition of all three 2,4-hexadiene isomers 7, 8, and 9 to C60 was observed (the trans stereochemistry in the cyclobutane ring predominates in all cases), while the unreactive double bond retained its stereochemical integrity in the adducts. The cis double bond of 9 is 1.5 times more reactive than the trans. The [2 + 2] photocycloaddition of (E)-2,4-dimethyl-2,4-hexadiene (10) to C60 is regiospecific, affording two diastereomeric adducts, 10a and 10b, by addition on the methyl monosubstituted terminal double bond. These results, when taken in conjunction with the small inverse intramolecular secondary isotope effect (k(H)/k(D) = 0.90 ± 0.05) in the [2 + 2] photocycloaddition of 1-d6 to C60, favor the formation of an open biradical intermediate in the rate- determining step.en
dc.sourceJournal of the American Chemical Societyen
dc.source.urihttps://www.scopus.com/inward/record.uri?eid=2-s2.0-0032582096&doi=10.1021%2fja981377w&partnerID=40&md5=48913bfb39be920315574e8ee0bf11a7
dc.subjectarticleen
dc.subjectsynthesisen
dc.subjectchemical bonden
dc.subjectstereospecificityen
dc.subjectreaction analysisen
dc.subjectproton nuclear magnetic resonanceen
dc.subjectfullerene derivativeen
dc.subjectstereochemistryen
dc.subjectphotochemistryen
dc.subjectcarbon nuclear magnetic resonanceen
dc.subjectalkadieneen
dc.subjectisotopeen
dc.subject1,3 butadiene derivativeen
dc.subjectalkyneen
dc.subjectdeuteriumen
dc.subjectdiastereoisomeren
dc.subjectphotooxidationen
dc.titleA new [2 + 2] functionalization of C60 with alkyl-substituted 1,3- butadienes: A mechanistic approach. Stereochemistry and isotope effectsen
dc.typeinfo:eu-repo/semantics/article
dc.identifier.doi10.1021/ja981377w
dc.description.volume120
dc.description.issue38
dc.description.startingpage9911
dc.description.endingpage9920
dc.author.faculty002 Σχολή Θετικών και Εφαρμοσμένων Επιστημών / Faculty of Pure and Applied Sciences
dc.author.departmentΤμήμα Χημείας / Department of Chemistry
dc.type.uhtypeArticleen
dc.description.notes<p>Cited By :38</p>en
dc.source.abbreviationJ.Am.Chem.Soc.en
dc.contributor.orcidChronakis, Nikos [0000-0002-2726-5290]
dc.contributor.orcidOrfanopoulos, Michael [0000-0002-7785-2071]
dc.gnosis.orcid0000-0002-2726-5290
dc.gnosis.orcid0000-0002-7785-2071


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