Gas-phase Nucleophilic Reactions Of Ge(och3)4: Experimental And Computational Characterization Of Pentacoordinated Ge Anions

dc.creatorMorgon N.H.
dc.creatorXavier L.A.
dc.creatorRiveros J.M.
dc.date2000
dc.date2015-06-30T19:50:40Z
dc.date2015-11-26T14:47:10Z
dc.date2015-06-30T19:50:40Z
dc.date2015-11-26T14:47:10Z
dc.date.accessioned2018-03-28T21:57:23Z
dc.date.available2018-03-28T21:57:23Z
dc.identifier
dc.identifierInternational Journal Of Mass Spectrometry. , v. 195-196, n. , p. 363 - 375, 2000.
dc.identifier13873806
dc.identifier10.1016/S1387-3806(99)00189-X
dc.identifierhttp://www.scopus.com/inward/record.url?eid=2-s2.0-0034695377&partnerID=40&md5=40550dbe828fcc1f4ed39e8089f78f06
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/107240
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/107240
dc.identifier2-s2.0-0034695377
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1253157
dc.descriptionThe gas-phase ion/molecule reactions of F- and CH3O- with Ge(OCH3)4 have been investigated by Fourier transform ion cyclotron mass spectrometry. Both nucleophiles react preferentially by an addition mechanism to yield XGe(OCH3)4/- (X = F, OCH3) complexes that are identified as typical pentacoordinated Ge species. Pentacoordinated Ge adducts formed with excess internal energy can undergo elimination of formaldehyde to yield HGe(OCH3)4/-, or further elimination processes that result in the formation of germyl anions like Ge(OCH3)3/-. Other minor product ions are also observed which can be attributed to the intermediacy of a pentacoordinated adduct. Dissociation of the XGe(OCH3)4/- anions induced by infrared multiphoton excitation leads to sequential losses of formaldehyde and gives rise to different germyl anions like Ge(OCH3)3/-, HGe(OCH3)2/-, and H2GeOCH3/-. The XGe(OCH3)4/- and germyl anions react readily with BF3 through successive methoxide-fluoride exchange and this reaction provides a gas-phase synthetic pathway for multiply fluorinated Ge anions. Ab initio calculations performed on model pentacoordinated species F(n+1)Ge(OH)(4-n)/- (n = 0-4) reveal that addition of a fluoride ion on hydroxygermanes occurs preferentially in the apical position of a trigonal bipyramid. The fluoride affinity of the prototype molecule Ge(OH)4 is calculated to be 60.9 kcal mol-1, and fluoride affinity increases monotonically with increasing fluorine substitution. The fluoride affinity of GeF4 is calculated to be 79 kcal mol-1. Similar calculations also predict an unusually high hydride affinity (60 kcal mol-1) for Ge(OH)4 with the hydride occupying an equatorial position. (C) 2000 Elsevier Science B.V.
dc.description195-196
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dc.description363
dc.description375
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dc.languageen
dc.publisher
dc.relationInternational Journal of Mass Spectrometry
dc.rightsfechado
dc.sourceScopus
dc.titleGas-phase Nucleophilic Reactions Of Ge(och3)4: Experimental And Computational Characterization Of Pentacoordinated Ge Anions
dc.typeArtículos de revistas


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