Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies
Autor(a) principal: | |
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Data de Publicação: | 2011 |
Outros Autores: | , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10400.26/21981 |
Resumo: | The 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. |
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Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studiesThe 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.Repositório ComumGamelas ou Carla A. Gamelas, CarlaBandeira, NunoPereira, CláudiaCalhorda, Maria JoséHerdtweck, EberhardtMachuqueiro, MiguelRomão, CarlosVeiros, Luís2018-03-13T14:54:42Z20112011-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.26/21981engGamelas, 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.10.1039/C1DT10607Dmetadata only accessinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-11-21T09:53:30Zoai:comum.rcaap.pt:10400.26/21981Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T23:09:22.936633Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies |
title |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies |
spellingShingle |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies Gamelas ou Carla A. Gamelas, Carla |
title_short |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies |
title_full |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies |
title_fullStr |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies |
title_full_unstemmed |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies |
title_sort |
Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C–S activation of trithiacyclononane: Experimental and theoretical studies |
author |
Gamelas ou Carla A. Gamelas, Carla |
author_facet |
Gamelas ou Carla A. Gamelas, Carla Bandeira, Nuno Pereira, Cláudia Calhorda, Maria José Herdtweck, Eberhardt Machuqueiro, Miguel Romão, Carlos Veiros, Luís |
author_role |
author |
author2 |
Bandeira, Nuno Pereira, Cláudia Calhorda, Maria José Herdtweck, Eberhardt Machuqueiro, Miguel Romão, Carlos Veiros, Luís |
author2_role |
author author author author author author author |
dc.contributor.none.fl_str_mv |
Repositório Comum |
dc.contributor.author.fl_str_mv |
Gamelas ou Carla A. Gamelas, Carla Bandeira, Nuno Pereira, Cláudia Calhorda, Maria José Herdtweck, Eberhardt Machuqueiro, Miguel Romão, Carlos Veiros, Luís |
description |
The 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. |
publishDate |
2011 |
dc.date.none.fl_str_mv |
2011 2011-01-01T00:00:00Z 2018-03-13T14:54:42Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
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info:eu-repo/semantics/article |
format |
article |
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publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10400.26/21981 |
url |
http://hdl.handle.net/10400.26/21981 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Gamelas, 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. 10.1039/C1DT10607D |
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metadata only access info:eu-repo/semantics/openAccess |
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metadata only access |
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openAccess |
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application/pdf |
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