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Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies

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dc.contributor.authorGamelas ou Carla A. Gamelas, Carla
dc.contributor.authorBandeira, Nuno
dc.contributor.authorPereira, Cláudia
dc.contributor.authorCalhorda, Maria José
dc.contributor.authorHerdtweck, Eberhardt
dc.contributor.authorMachuqueiro, Miguel
dc.contributor.authorRomão, Carlos
dc.contributor.authorVeiros, Luís
dc.date.accessioned2018-03-13T14:54:42Z
dc.date.available2018-03-13T14:54:42Z
dc.date.issued2011
dc.description.abstractThe macrocycle 1,4,7-trithiacyclononane (ttcn) reacts with [(η5-Ind)Mo(CO)2(NCMe)2]+ (or [(η5-Ind)Mo(CO)2(κ2-dme)]+) to give [(η3-Ind)Mo(CO)2(κ3-ttcn)]+ as the BF4− salt (1), but its reaction with [(η5-Ind)Mo(CO)2(C3H6)(FBF3)] affords the C–S bond cleavage product [(η5-Ind)Mo(CO)(κ3-1,4,7-trithiaheptanate)]BF4 (6), which has been characterised by X-ray crystallography (Ind = C9H7, indenyl). In contrast to ttcn, the macrocycles 1,3,5-trithiane (tt) and 1,4,7,10-tetrathiacyclododecane (ttcd) fail to induce changes in the coordination mode of indenyl: tt and ttcd react with [(η5-Ind)Mo(CO)2(NCMe)2]+ (or [(η5-Ind)Mo(CO)2(κ2-dme)]+) to give [(η5-Ind)Mo(CO)2(κ2-tt)]+ (2), characterised by X-ray crystallography, and [(η5-Ind)Mo(CO)2(κ2-ttcd)]+ (3), respectively. The cyclopentadienyl (Cp = C5H5) analogues [(η5-CpMo(CO)2(κ2-tt)]+ (4) and [(η5-CpMo(CO)2(κ2-ttcn)]+ (5) have also been synthesised and 5 characterised by X-ray crystallography. DFT calculations showed that the η5-Ind/Cp coordination mode is always the most stable. However, a molecular dynamics study of the macrocycles conformations revealed that the major conformer of ttcn was a chair, which favoured κ3 coordination. As indenyl complexes undergo slippage with a small barrier (<10 kcal mol−1), the kinetically preferred species [(η3-Ind)Mo(CO)2(κ3-ttcn)]+ (1) is the observed one. The conversion to 6 proceeds stepwise, with loss of ethylene followed by loss of CO, as calculated by DFT, with a barrier of 38.7 kcal mol−1, consistent with the slow uncatalysed reaction.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationGamelas, C., Bandeira, N., Pereira, C., Calhorda, M. J., Herdtweck, E., Machuqueiro, M. … Veiros, L.(2011). Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies. Dalton Transactions, 40, pp. 10513 - 10513. doi: 10.1039/C1DT10607D.pt_PT
dc.identifier.doi10.1039/C1DT10607Dpt_PT
dc.identifier.urihttp://hdl.handle.net/10400.26/21981
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.titleIndenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studiespt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage10513pt_PT
oaire.citation.startPage10513pt_PT
oaire.citation.titleJournal- Chemical Society Dalton Transactionspt_PT
person.familyNameGamelas Albuquerque Pinto Reis
person.givenNameCarla Alexandra
person.identifier.ciencia-id2219-54F2-BB9D
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
relation.isAuthorOfPublicationa02aa459-55c4-4506-b8f2-5189e5c13124
relation.isAuthorOfPublication.latestForDiscoverya02aa459-55c4-4506-b8f2-5189e5c13124

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