Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel
dc.contributor.author | Iamamoto, Y. | |
dc.contributor.author | Ciuffi, K. J. | |
dc.contributor.author | Sacco, H. C. | |
dc.contributor.author | Iwamoto, L. S. | |
dc.contributor.author | Nascimento, O. R. | |
dc.contributor.author | Prado, CMC | |
dc.contributor.institution | Universidade de São Paulo (USP) | |
dc.contributor.institution | Universidade Estadual Paulista (Unesp) | |
dc.date.accessioned | 2014-05-20T15:27:03Z | |
dc.date.available | 2014-05-20T15:27:03Z | |
dc.date.issued | 1997-03-07 | |
dc.description.abstract | In this work we have made use of the study of the interaction between Fe(TDCPP)(+) and the axial ligands OH- and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 X 10(-6) mol Fe(TDCPP)(+)/g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin (FeP)-P-III species. In Fe(TDCPP)IPG 1 (containing 1.1 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-4) mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP)(+) is present as a mixture of low-spin (FeP)-P-III and (FeP)-P-II species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the (FeP)-P-III to the support partially blocks the reaction between Fe(TDCPP)(+) and PhIO, thus leading to the formation of only a small amount of the active species Fe-IV(OP+, while the (FeP)-P-II species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP)(+) and decreasing the amount of imidazole in the support led to the obtention of high-spin (FeP)-P-III EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-5) mol imidazole/g of IPG), together with low-spin (FeP)-P-III species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it. | en |
dc.description.affiliation | UNIV SAO PAULO,INST FIS SAO CARLOS,SAO CARLOS,SP,BRAZIL | |
dc.description.affiliation | UNESP,INST QUIM,ARARAQUARA,SP,BRAZIL | |
dc.description.affiliationUnesp | UNESP,INST QUIM,ARARAQUARA,SP,BRAZIL | |
dc.format.extent | 405-420 | |
dc.identifier | http://dx.doi.org/10.1016/S1381-1169(96)00342-1 | |
dc.identifier.citation | Journal of Molecular Catalysis A-chemical. Amsterdam: Elsevier B.V., v. 116, n. 3, p. 405-420, 1997. | |
dc.identifier.doi | 10.1016/S1381-1169(96)00342-1 | |
dc.identifier.issn | 1381-1169 | |
dc.identifier.uri | http://hdl.handle.net/11449/37099 | |
dc.identifier.wos | WOS:A1997WL78200012 | |
dc.language.iso | eng | |
dc.publisher | Elsevier B.V. | |
dc.relation.ispartof | Journal of Molecular Catalysis A: Chemical | |
dc.relation.ispartofjcr | 4.397 | |
dc.rights.accessRights | Acesso restrito | |
dc.source | Web of Science | |
dc.subject | cyclohexane | pt |
dc.subject | imidazole propyl gel | pt |
dc.subject | iron(III)porphyrin | pt |
dc.subject | 2,6-dichlorophenyl porphyrin | pt |
dc.subject | oxidation | pt |
dc.subject | porphyrin | pt |
dc.subject | supported catalysts | pt |
dc.title | Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel | en |
dc.type | Artigo | |
dcterms.license | http://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy | |
dcterms.rightsHolder | Elsevier B.V. | |
unesp.author.orcid | 0000-0001-8270-0286[2] | |
unesp.author.orcid | 0000-0003-0761-5086[1] |
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