Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones
| Autor(a) principal: | |
|---|---|
| Data de Publicação: | 2007 |
| Outros Autores: | , , , , , |
| Tipo de documento: | Artigo |
| Idioma: | eng |
| Título da fonte: | Repositório Institucional da UFBA |
| Texto Completo: | http://repositorio.ufba.br/ri/handle/ri/14720 |
Resumo: | Texto completo: acesso restrito. p.1117–1122 |
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Garden, Nanci Camara de LucasCorrea, Rodrigo JoseAlbuquerque, Ana Carla CruzFirme, Caio LimaGarden, Simon JohnBertoti, Ada RuthFerreira, José Carlos NettoGarden, Nanci Camara de LucasCorrea, Rodrigo JoseAlbuquerque, Ana Carla CruzFirme, Caio LimaGarden, Simon JohnBertoti, Ada RuthFerreira, José Carlos Netto2014-03-11T14:28:43Z20071089-5639http://repositorio.ufba.br/ri/handle/ri/14720v. 111, n. 6Texto completo: acesso restrito. p.1117–1122Laser flash photolysis (LFP) studies, atoms in molecules (AIM) studies, and density functional theory (DFT) calculations have been performed in order to study the mechanism of the hydrogen abstraction by α-diketones in the presence of phenols. Laser irradiation of a degassed solution of 1,2-diketopyracene in acetonitrile resulted in the formation of a readily detectable transient with absorption at 610 nm, but with very low absorptivity. This transient decays with a lifetime of around 2 μs. The quenching rate constant for substituted phenols, kq, ranged from 1.10 × 108 L mol-1 s-1 (4-cyanophenol) to 3.87 × 109 L mol-1 s-1 (4-hydroxyphenol). The Hammett plot for the reaction of the triplet of 1,2-diketopyracene with phenols gave a reaction constant ρ = −0.9. DFT calculations (UB3LYP/6-311++G**//UB3LYP/6-31G*) of the triplet complex ketone−phenol revealed that hydrogen transfer has predominantly occurred and that the reaction with α-diketones are generally 7 kcal/mol less endothermic than the respective reactions of the monoketones. These results together with the geometries obtained from the DFT calculations, natural bond order (NBO) analysis, and AIM results indicate that hydrogen abstraction for α-diketones is facilitated by the electrophilicity of the ketone, instead of neighboring group participation by the second carbonyl group.Submitted by Suelen Reis (suziy.ellen@gmail.com) on 2014-03-11T14:28:43Z No. of bitstreams: 1 jp065675o.pdf: 103488 bytes, checksum: 28467a18d86068582af192372ced1977 (MD5)Made available in DSpace on 2014-03-11T14:28:43Z (GMT). No. of bitstreams: 1 jp065675o.pdf: 103488 bytes, checksum: 28467a18d86068582af192372ced1977 (MD5) Previous issue date: 2007http://dx.doi.org/10.1021/jp065675oreponame:Repositório Institucional da UFBAinstname:Universidade Federal da Bahia (UFBA)instacron:UFBALaser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketonesJournal of Physical Chemistry Ainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article10000-01-01info:eu-repo/semantics/openAccessengORIGINALjp065675o.pdfjp065675o.pdfapplication/pdf103488https://repositorio.ufba.br/bitstream/ri/14720/1/jp065675o.pdf28467a18d86068582af192372ced1977MD51LICENSElicense.txtlicense.txttext/plain1345https://repositorio.ufba.br/bitstream/ri/14720/2/license.txt0d4b811ef71182510d2015daa7c8a900MD52TEXTjp065675o.pdf.txtjp065675o.pdf.txtExtracted texttext/plain31152https://repositorio.ufba.br/bitstream/ri/14720/3/jp065675o.pdf.txtcb316a8461d36223423dae16592f0d94MD53ri/147202022-07-05 14:03:11.121oai:repositorio.ufba.br:ri/14720VGVybW8gZGUgTGljZW4/YSwgbj9vIGV4Y2x1c2l2bywgcGFyYSBvIGRlcD9zaXRvIG5vIFJlcG9zaXQ/cmlvIEluc3RpdHVjaW9uYWwgZGEgVUZCQS4KCiBQZWxvIHByb2Nlc3NvIGRlIHN1Ym1pc3M/byBkZSBkb2N1bWVudG9zLCBvIGF1dG9yIG91IHNldSByZXByZXNlbnRhbnRlIGxlZ2FsLCBhbyBhY2VpdGFyIAplc3NlIHRlcm1vIGRlIGxpY2VuP2EsIGNvbmNlZGUgYW8gUmVwb3NpdD9yaW8gSW5zdGl0dWNpb25hbCBkYSBVbml2ZXJzaWRhZGUgRmVkZXJhbCBkYSBCYWhpYSAKbyBkaXJlaXRvIGRlIG1hbnRlciB1bWEgYz9waWEgZW0gc2V1IHJlcG9zaXQ/cmlvIGNvbSBhIGZpbmFsaWRhZGUsIHByaW1laXJhLCBkZSBwcmVzZXJ2YT8/by4gCkVzc2VzIHRlcm1vcywgbj9vIGV4Y2x1c2l2b3MsIG1hbnQ/bSBvcyBkaXJlaXRvcyBkZSBhdXRvci9jb3B5cmlnaHQsIG1hcyBlbnRlbmRlIG8gZG9jdW1lbnRvIApjb21vIHBhcnRlIGRvIGFjZXJ2byBpbnRlbGVjdHVhbCBkZXNzYSBVbml2ZXJzaWRhZGUuCgogUGFyYSBvcyBkb2N1bWVudG9zIHB1YmxpY2Fkb3MgY29tIHJlcGFzc2UgZGUgZGlyZWl0b3MgZGUgZGlzdHJpYnVpPz9vLCBlc3NlIHRlcm1vIGRlIGxpY2VuP2EgCmVudGVuZGUgcXVlOgoKIE1hbnRlbmRvIG9zIGRpcmVpdG9zIGF1dG9yYWlzLCByZXBhc3NhZG9zIGEgdGVyY2Vpcm9zLCBlbSBjYXNvIGRlIHB1YmxpY2E/P2VzLCBvIHJlcG9zaXQ/cmlvCnBvZGUgcmVzdHJpbmdpciBvIGFjZXNzbyBhbyB0ZXh0byBpbnRlZ3JhbCwgbWFzIGxpYmVyYSBhcyBpbmZvcm1hPz9lcyBzb2JyZSBvIGRvY3VtZW50bwooTWV0YWRhZG9zIGVzY3JpdGl2b3MpLgoKIERlc3RhIGZvcm1hLCBhdGVuZGVuZG8gYW9zIGFuc2Vpb3MgZGVzc2EgdW5pdmVyc2lkYWRlIGVtIG1hbnRlciBzdWEgcHJvZHU/P28gY2llbnQ/ZmljYSBjb20gCmFzIHJlc3RyaT8/ZXMgaW1wb3N0YXMgcGVsb3MgZWRpdG9yZXMgZGUgcGVyaT9kaWNvcy4KCiBQYXJhIGFzIHB1YmxpY2E/P2VzIHNlbSBpbmljaWF0aXZhcyBxdWUgc2VndWVtIGEgcG9sP3RpY2EgZGUgQWNlc3NvIEFiZXJ0bywgb3MgZGVwP3NpdG9zIApjb21wdWxzP3Jpb3MgbmVzc2UgcmVwb3NpdD9yaW8gbWFudD9tIG9zIGRpcmVpdG9zIGF1dG9yYWlzLCBtYXMgbWFudD9tIGFjZXNzbyBpcnJlc3RyaXRvIAphbyBtZXRhZGFkb3MgZSB0ZXh0byBjb21wbGV0by4gQXNzaW0sIGEgYWNlaXRhPz9vIGRlc3NlIHRlcm1vIG4/byBuZWNlc3NpdGEgZGUgY29uc2VudGltZW50bwogcG9yIHBhcnRlIGRlIGF1dG9yZXMvZGV0ZW50b3JlcyBkb3MgZGlyZWl0b3MsIHBvciBlc3RhcmVtIGVtIGluaWNpYXRpdmFzIGRlIGFjZXNzbyBhYmVydG8uCg==Repositório InstitucionalPUBhttp://192.188.11.11:8080/oai/requestopendoar:19322022-07-05T17:03:11Repositório Institucional da UFBA - Universidade Federal da Bahia (UFBA)false |
| dc.title.pt_BR.fl_str_mv |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones |
| dc.title.alternative.pt_BR.fl_str_mv |
Journal of Physical Chemistry A |
| title |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones |
| spellingShingle |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones Garden, Nanci Camara de Lucas |
| title_short |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones |
| title_full |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones |
| title_fullStr |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones |
| title_full_unstemmed |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones |
| title_sort |
Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic α-diketones |
| author |
Garden, Nanci Camara de Lucas |
| author_facet |
Garden, Nanci Camara de Lucas Correa, Rodrigo Jose Albuquerque, Ana Carla Cruz Firme, Caio Lima Garden, Simon John Bertoti, Ada Ruth Ferreira, José Carlos Netto |
| author_role |
author |
| author2 |
Correa, Rodrigo Jose Albuquerque, Ana Carla Cruz Firme, Caio Lima Garden, Simon John Bertoti, Ada Ruth Ferreira, José Carlos Netto |
| author2_role |
author author author author author author |
| dc.contributor.author.fl_str_mv |
Garden, Nanci Camara de Lucas Correa, Rodrigo Jose Albuquerque, Ana Carla Cruz Firme, Caio Lima Garden, Simon John Bertoti, Ada Ruth Ferreira, José Carlos Netto Garden, Nanci Camara de Lucas Correa, Rodrigo Jose Albuquerque, Ana Carla Cruz Firme, Caio Lima Garden, Simon John Bertoti, Ada Ruth Ferreira, José Carlos Netto |
| description |
Texto completo: acesso restrito. p.1117–1122 |
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2007 |
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2007 |
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2014-03-11T14:28:43Z |
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http://repositorio.ufba.br/ri/handle/ri/14720 |
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1089-5639 |
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v. 111, n. 6 |
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1089-5639 v. 111, n. 6 |
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http://repositorio.ufba.br/ri/handle/ri/14720 |
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