Zeolite Activation Of Organometallics: Revisiting Substitution Kinetics Of [mo(co)6] With Chemisorbed Pme3 In Dehydrated Na 56y Zeolite

dc.creatorFernandez A.L.
dc.creatorHao J.
dc.creatorParkes R.L.
dc.creatorPoe A.J.
dc.creatorVichi E.J.S.
dc.date2008
dc.date2015-06-30T19:28:06Z
dc.date2015-11-26T14:44:31Z
dc.date2015-06-30T19:28:06Z
dc.date2015-11-26T14:44:31Z
dc.date.accessioned2018-03-28T21:53:23Z
dc.date.available2018-03-28T21:53:23Z
dc.identifier
dc.identifierJournal Of The Brazilian Chemical Society. , v. 19, n. 5, p. 862 - 871, 2008.
dc.identifier1035053
dc.identifier
dc.identifierhttp://www.scopus.com/inward/record.url?eid=2-s2.0-46749101743&partnerID=40&md5=fa873533501c0cda085644d271796622
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/106340
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/106340
dc.identifier2-s2.0-46749101743
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1252159
dc.descriptionReactions of [Mo(CO)6] under vacuum in α-cages of Na 56Y zeolite fully loaded with chemisorbed PMe3 form cis-[Mo(CO)4(PMe3)2] but mixtures of [Mo(CO)5(PMe3)] and cis-[Mo(CO)4(PMe 3)2] are formed under CO. Reactions under vacuum exhibit low enthalpic and very negative entropic factors (ΔH‡ = 71.4 ± 3.5 kJ mol-1 and ΔS‡ = -102 ± 11 J K-1 mol-1) compared with much higher enthalpic and positive entropic factors for CO dissociative reactions with P(n-Bu)3 in xylene observed elsewhere. Reaction at 66 °C under vacuum is ca.103 times faster than "spontaneous" CO dissociative reactions in solution. Intrazeolite substitution is concluded to occur by a "zeolite assisted" mechanism in which two oxide ions in the cavity walls simultaneously displace two neighbouring CO ligands from the [Mo(CO)6]. This contrasts with even lower enthalpy, and more negative entropy values, for simultaneous displacement of three neighbouring CO ligands in thermal decarbonylation reactions. The α-cages behave as multidentate anionic "zeolate" ligands with varying numbers of O2- ions participating to create highly ordered transition states. These results emphasize the high degree to which such kinetic studies can reveal intimate details of the nature of these activating effects. ©2008 Sociedade Brasileira de Química.
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dc.languageen
dc.publisher
dc.relationJournal of the Brazilian Chemical Society
dc.rightsaberto
dc.sourceScopus
dc.titleZeolite Activation Of Organometallics: Revisiting Substitution Kinetics Of [mo(co)6] With Chemisorbed Pme3 In Dehydrated Na 56y Zeolite
dc.typeArtículos de revistas


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