Adducts and dimers of SFn+ (n = 1-5) with benzene, acetonitrile, and pyridine. Gas-phase generation and ab initio structures and thermochemistry

dc.creatorSparrapan, R
dc.creatorMendes, MA
dc.creatorEberlin, MN
dc.date1999
dc.date36951
dc.date2014-12-02T16:30:51Z
dc.date2015-11-26T17:40:49Z
dc.date2014-12-02T16:30:51Z
dc.date2015-11-26T17:40:49Z
dc.date.accessioned2018-03-29T00:22:32Z
dc.date.available2018-03-29T00:22:32Z
dc.identifierInternational Journal Of Mass Spectrometry. Elsevier Science Bv, v. 182, n. 369, n. 380, 1999.
dc.identifier1387-3806
dc.identifierWOS:000078874700036
dc.identifier10.1016/S1387-3806(98)14235-5
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/76724
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/76724
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/76724
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1286833
dc.descriptionPentaquadrupole (QqQqQ) mass spectrometry is used to explore the abilities of gaseous SFn+ (n = 1-5) ions to form adducts and dimers with three pi-electron rich molecules-benzene, acetonitrile, and pyridine, whereas ab initio calculations estimate most feasible structures, bond dissociation energies (BDEs), and reaction enthalpies of the observed products. With benzene, SF+ reacts by net H-by-SF+. replacement. As suggested by the calculations, this novel benzene reaction forms ionized benzenesulfenyl fluoride, C6H5-SF+., via a Wheland-type intermediate that spontaneously loses a H atom. SF3+ forms a rare, loosely bonded n complex with benzene, [Bz ... SF3](+), which is stable toward both H and HF loss. No dimer. Bz(2)SF(3)(+), is formed. According to calculations, an unsymmetrically bonded, pi-coordinated Bz(2)SF(3)(+) dimer exists, i.e. (Bz-SF(3 ...)Bz)(+) but its formation from [Bz ... SF3](+) is endothermic; hence, thermodynamically unfavorable. With acetonitrile, SF2+., SF3+, and SF5+ form both adducts and dimers. CH3-C-.=N-SF2+ (a new distonic ion) and CH3CN-SF5+ are covalently bonded, but CH3CN ... SF3+ is loosely bonded. The binding natures of the acetonitrile adducts are reflected in the dimers; [CH3CN-SF2 NCCH3](+.) and [CH3CN-SF5... NCCH3](+) are unsymmetrically bonded, whereas [CH3CN ... SF3... NCCH3](+) is symmetrically and loosely bonded. Such dimers as [CH3CN ... SF3... NCCH3](+) are ideal for measurements of ion affinity via the Cooks' kinetic method. With pyridine, only SF3+ forms adduct and dimer. Py-SF3+ is covalently bonded through nitrogen; [Py ... SF3... Py](+) is loosely but unsymmetrically bonded. The unsymmetric 2.28 and 2.44 Angstrom long N-S bonds in [Py ... SF3... Py](+), which are expected to rapidly interconvert, result Likely from steric hindrance that forces orthogonal alignment of the two pyridine rings. Most observed adducts and dimers display relatively high BDEs, i.e. they are formed in thermodynamically favorable reactions. The extents of dissociation of the adducts and dimers observed in MS3 experiments reflect the structures and BDEs predicted by the calculations. (C) 1999 Elsevier Science B.V.
dc.description182
dc.description369
dc.description380
dc.languageen
dc.publisherElsevier Science Bv
dc.publisherAmsterdam
dc.publisherHolanda
dc.relationInternational Journal Of Mass Spectrometry
dc.relationInt. J. Mass Spectrom.
dc.rightsfechado
dc.rightshttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy
dc.sourceWeb of Science
dc.subjectSF6
dc.subjectSFn+
dc.subjectSF5+
dc.subjectSF4+center dot
dc.subjectSF3+
dc.subjectSF2+center dot
dc.subjectSF+
dc.subjection/molecule reactions
dc.subjectpentaquadrupole mass spectrometry
dc.subjectMass-spectrometry
dc.subjectKinetic Method
dc.subjectIons
dc.subjectAffinities
dc.titleAdducts and dimers of SFn+ (n = 1-5) with benzene, acetonitrile, and pyridine. Gas-phase generation and ab initio structures and thermochemistry
dc.typeArtículos de revistas


Este ítem pertenece a la siguiente institución