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Amino-Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole-Saccharinate as Probed by Matrix Isolation Infrared Spectroscopy

2013Journal article Restricted access
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dc.contributor.authorIsmael, Amin
dc.contributor.authorGómez-Zavaglia, A.
dc.contributor.authorBorba, A.
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.contributor.authorFausto, R.
dc.date.accessioned2014-06-06T14:59:27Z
dc.date.available2014-06-06T14:59:27Z
dc.date.issued2013
dc.date.updated2014-05-30T14:52:36Z
dc.description.abstractThe amino−imino tautomerization of the nitrogen-linked conjugate 2-methyltetrazole-saccharinate (2MTS) was observed upon sublimation of the compound in vacuo. As shown previously by X-ray diffraction [Ismael, A.; Paixão, J. A.; Fausto, R.; Cristiano, M. L. S. J. Mol. Struct., 2011, 1023, 128−142], in the crystalline phase the compound exists in an amino-bridged tautomeric form. Infrared spectroscopic investigation of a cryogenic matrix prepared after sublimation of a crystalline sample of 2MTS and deposition of the sublimate together with argon (in ∼1:1000 molar ratio) onto an IR-transparent cold (15 K) substrate, revealed that the form of 2MTS present in the matrix corresponds to the theoretically predicted most stable imino-bridged tautomer. In this tautomer, the labile hydrogen atom is connected to the saccharine nitrogen, and the two heterocyclic fragments are linked by an imino moiety in which the double-bond is established with the carbon atom belonging to the saccharyl fragment. The observed isomeric form of this tautomer is characterized by a zusammen (Z) arrangement of the two rings around the CN bond of the bridging group and an intramolecular NH···N hydrogen bond. The experimental IR spectrum of the matrix-isolated 2MTS has been fully assigned based on the calculated spectra for the two most stable conformers of this tautomer. A mechanism for the conversion of the tautomeric form existing in the crystal into that present in the gas phase is proposed. As a basis for the interpretation of the experimental results, a detailed theoretical [at the DFT(B3LYP) level of approximation with the 6-31+ +G(d,p) and 6-311++G(3df,3pd)] study of the potential energy surface of the compound was performed.por
dc.identifier.citationIsmael, Amin; Gómez-Zavaglia, Andrea; Borba, Ana; Cristiano, Maria de Lurdes Santos; Fausto, Rui. Amino-Imino tautomerization upon in vacuo sublimation of 2-methyltetrazole-saccharinate as probed by matrix isolation infrared spectroscopy, The Journal of Physical Chemistry A, 117, 15, 3190 -3197, 2013.por
dc.identifier.doihttp://dx.doi.org/10.1021/jp401360c |
dc.identifier.issn1089-5639
dc.identifier.otherAUT: MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/4225
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherAmerican Chemical Societypor
dc.relation.publisherversionhttp://pubs.acs.orgpor
dc.titleAmino-Imino Tautomerization upon in Vacuo Sublimation of 2-Methyltetrazole-Saccharinate as Probed by Matrix Isolation Infrared Spectroscopypor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage3197por
oaire.citation.issue15por
oaire.citation.startPage3190por
oaire.citation.titleThe Journal of Physical Chemistry Apor
oaire.citation.volume117por
person.familyNameIsmael
person.familyNameCristiano
person.givenNameAmin
person.givenNameMaria de Lurdes
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-7346-5998
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridA-8153-2013
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id35203489500
person.identifier.scopus-author-id9238724800
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublicationfa01ef7f-7a2a-4f74-a405-714360b862f3
relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isAuthorOfPublication.latestForDiscoveryb16751a6-748e-44b0-9c59-058cbd5b2cc3

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