Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados)
Autor(a) principal: | |
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Data de Publicação: | 2010 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/6261 |
Resumo: | In this thesis it were studied substitution reactions in ruthenium complexes of the type cis-[RuCl2(P-P)(N-N)] and cis-[RuCl2(dppb)(N-O)] (P-P = dppm, dppe, dppp and dppb; N-N = bipy, Me-bipy, MeO-bipy, Cl-bipy and fen; N-O = 2-acpy, 2-bzpy and 2- dpk). For all complexes, in a period of 24 hours, there was only the substitution of a chloride (Cl-) coordinated to the metal. The ligands used in substitution reactions and kinetic studies were: py, 4-pic and coordenant solvents (CH3CN and PhCN). Only the Cl- trans positioned to P of diphosphines was labilized giving rise to the entering ligand, confirming the greater trans effect of phosphine ligands in relation to N-N and N-O. The mechanism attributed to substitution reactions was dissociative because the reactions do not show dependence of ligand entry. DFT calculations showed the effective participation of the Cl atom trans to the P atom of the diphosphines in the formation of the HOMO orbital. This fact shows that the reactivity of Cl atoms is different and they can be replaced selectively. Good linearity was observed for the percentage of participation of d orbitals of ruthenium in the formation of HOMO for the dissociation of Cl- complex indicating that the strength of the Ru-Cl- bond is due to the direct interaction of the orbitals of Cl- and the d orbitals of ruthenium. Exploratory studies using irradiation of light at fixed wavelengths were performed to study possible influence of the effect of the exchange rate of Cl- and also on the isomerization reaction trans/cis-[RuCl2(dppb)(bipy)]. An increase in the rate of exchange reaction was observed in the kinetics of substitution. In the isomerization processes were not observed. The substitution reactions of Cl- in the complexes cis- [RuCl2(dppb)(N-N)] (N-N = bipy and phen) by nitrile ligands (e.g. PhCN and CH3CN), lead to the formation of complexes in which trans ligands L were coordinated by the nitrogen atom of the ligands N-N in the final complex. However, studies of 31P{1H} NMR and cyclic voltammetry confirmed that the reactions take place initially with the replacement of L trans to P atom followed by an isomerization process. This is attributed to the strong competition of π between nitrile and phosphine ligands, and its final position is determined by this effect. |
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Nascimento, Fábio Batista doBatista, Alzir Azevedohttp://lattes.cnpq.br/6469642481998660http://lattes.cnpq.br/802264341535103904768317-8f28-4e8a-8b1c-e3065a74a87a2016-06-02T20:34:42Z2013-06-072016-06-02T20:34:42Z2010-10-14NASCIMENTO, Fábio Batista do. Kinetics ans Photochemical studies of Ru(II) compounds with Diimine and Diphosphine ligands of general formulae cis-[RuCl2(PP)(N-N)] (P-P = Diphosphines and N-N Bidentades N-Heterociclic ligands). 2010. 214 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010.https://repositorio.ufscar.br/handle/ufscar/6261In this thesis it were studied substitution reactions in ruthenium complexes of the type cis-[RuCl2(P-P)(N-N)] and cis-[RuCl2(dppb)(N-O)] (P-P = dppm, dppe, dppp and dppb; N-N = bipy, Me-bipy, MeO-bipy, Cl-bipy and fen; N-O = 2-acpy, 2-bzpy and 2- dpk). For all complexes, in a period of 24 hours, there was only the substitution of a chloride (Cl-) coordinated to the metal. The ligands used in substitution reactions and kinetic studies were: py, 4-pic and coordenant solvents (CH3CN and PhCN). Only the Cl- trans positioned to P of diphosphines was labilized giving rise to the entering ligand, confirming the greater trans effect of phosphine ligands in relation to N-N and N-O. The mechanism attributed to substitution reactions was dissociative because the reactions do not show dependence of ligand entry. DFT calculations showed the effective participation of the Cl atom trans to the P atom of the diphosphines in the formation of the HOMO orbital. This fact shows that the reactivity of Cl atoms is different and they can be replaced selectively. Good linearity was observed for the percentage of participation of d orbitals of ruthenium in the formation of HOMO for the dissociation of Cl- complex indicating that the strength of the Ru-Cl- bond is due to the direct interaction of the orbitals of Cl- and the d orbitals of ruthenium. Exploratory studies using irradiation of light at fixed wavelengths were performed to study possible influence of the effect of the exchange rate of Cl- and also on the isomerization reaction trans/cis-[RuCl2(dppb)(bipy)]. An increase in the rate of exchange reaction was observed in the kinetics of substitution. In the isomerization processes were not observed. The substitution reactions of Cl- in the complexes cis- [RuCl2(dppb)(N-N)] (N-N = bipy and phen) by nitrile ligands (e.g. PhCN and CH3CN), lead to the formation of complexes in which trans ligands L were coordinated by the nitrogen atom of the ligands N-N in the final complex. However, studies of 31P{1H} NMR and cyclic voltammetry confirmed that the reactions take place initially with the replacement of L trans to P atom followed by an isomerization process. This is attributed to the strong competition of π between nitrile and phosphine ligands, and its final position is determined by this effect.Nesta tese de doutorado foram estudadas reações de substituição em complexos de rutênio do tipo cis-[RuCl2(P-P)(N-N)] e cis-[RuCl2(dppb)(N-O)] (P-P = dppm, dppe, dppp e dppb; N-N = bipy, Me-bipy, MeO-bipy, Cl-bipy e fen; N-O = 2-acpy, 2-bzpy e 2-dpk). Para todos os complexos, num período de 24 horas, observou-se apenas a substituição de um cloreto (Cl-) coordenado ao metal. Os ligantes usados nas reações de substituição e nos estudos cinéticos foram: py, 4-pic e solventes coordenantes (CH3CN e PhCN). Apenas o Cl- trans posicionado ao átomo de P das bifosfinas foi labilizado, dando lugar ao ligante de entrada, confirmando o maior efeito trans da fosfina em relação aos ligantes N-N e N-O. O mecanismo atribuído para as reações de substituição foi dissociativo, pois as reações não apresentam dependência do ligante de entrada. Cálculos de DFT mostraram a participação efetiva, apenas do átomo de Cl trans ao átomo de P da bifosfina na formação dos orbitais HOMO. Este fato nos mostra que a reatividade desses átomos de Cl é diferente e os mesmos podem ser substituídos de maneira seletiva. Boa linearidade foi observada em relação à porcentagem de participação dos orbitais d do rutênio na formação de HOMO em relação às constantes de dissociação de Cl- nos complexos, indicando que a força da ligação Ru-Cl- é devido à interação direta dos orbitais de Cle os orbitais d do rutênio. Estudos exploratórios, utilizando irradiação de luz em comprimentos de onda fixados, foram realizados a fim de se observar o efeito da mesma na velocidade de troca de Cl- e também na reação de isomerização trans/cis-[RuCl2(dppb)(bipy). Apenas nas cinéticas de substituição foi observado um aumento na velocidade da reação de troca e nas reações de isomerização não observamos nenhum efeito. Nas reações de substituição de Cl- nos complexos cis- [RuCl2(dppb)(N-N)] (N-N = bipy e fen), pelos ligantes nitrila (PhCN e CH3CN), observou-se a formação de complexos onde o ligante L estava coordenado trans ao átomo de nitrogênio dos ligantes N-N no complexo final. Contudo, estudos de RMN 31P{1H} e voltametria cíclica confirmaram que a reação se dá, inicialmente com a substituição de L trans ao átomo de P seguido por uma isomerização. Este efeito foi xvii atribuído à forte competição π entre os ligantes nitrila e fosfínicos, sendo sua posição final decidida por este efeito.Universidade Federal de Sao Carlosapplication/pdfporUniversidade Federal de São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarBRQuímica inorgânicaComplexos de rutênioCinéticaReações de substituiçãoReatividade (Química)CIENCIAS EXATAS E DA TERRA::QUIMICAEstudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados)Kinetics ans Photochemical studies of Ru(II) compounds with Diimine and Diphosphine ligands of general formulae cis-[RuCl2(PP)(N-N)] (P-P = Diphosphines and N-N Bidentades N-Heterociclic ligands)info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis-1-1e62fb48f-fa23-4158-8d60-0b17f006946cinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINAL5167.pdfapplication/pdf5245657https://repositorio.ufscar.br/bitstream/ufscar/6261/1/5167.pdf48719a473b2a9e562a8d9723e6d08b69MD51TEXT5167.pdf.txt5167.pdf.txtExtracted texttext/plain0https://repositorio.ufscar.br/bitstream/ufscar/6261/4/5167.pdf.txtd41d8cd98f00b204e9800998ecf8427eMD54THUMBNAIL5167.pdf.jpg5167.pdf.jpgIM Thumbnailimage/jpeg11051https://repositorio.ufscar.br/bitstream/ufscar/6261/5/5167.pdf.jpgd971154eb6545f45684c7f86a856d50aMD55ufscar/62612023-09-18 18:30:35.701oai:repositorio.ufscar.br:ufscar/6261Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:30:35Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) |
dc.title.alternative.eng.fl_str_mv |
Kinetics ans Photochemical studies of Ru(II) compounds with Diimine and Diphosphine ligands of general formulae cis-[RuCl2(PP)(N-N)] (P-P = Diphosphines and N-N Bidentades N-Heterociclic ligands) |
title |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) |
spellingShingle |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) Nascimento, Fábio Batista do Química inorgânica Complexos de rutênio Cinética Reações de substituição Reatividade (Química) CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) |
title_full |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) |
title_fullStr |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) |
title_full_unstemmed |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) |
title_sort |
Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados) |
author |
Nascimento, Fábio Batista do |
author_facet |
Nascimento, Fábio Batista do |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8022643415351039 |
dc.contributor.author.fl_str_mv |
Nascimento, Fábio Batista do |
dc.contributor.advisor1.fl_str_mv |
Batista, Alzir Azevedo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/6469642481998660 |
dc.contributor.authorID.fl_str_mv |
04768317-8f28-4e8a-8b1c-e3065a74a87a |
contributor_str_mv |
Batista, Alzir Azevedo |
dc.subject.por.fl_str_mv |
Química inorgânica Complexos de rutênio Cinética Reações de substituição Reatividade (Química) |
topic |
Química inorgânica Complexos de rutênio Cinética Reações de substituição Reatividade (Química) CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In this thesis it were studied substitution reactions in ruthenium complexes of the type cis-[RuCl2(P-P)(N-N)] and cis-[RuCl2(dppb)(N-O)] (P-P = dppm, dppe, dppp and dppb; N-N = bipy, Me-bipy, MeO-bipy, Cl-bipy and fen; N-O = 2-acpy, 2-bzpy and 2- dpk). For all complexes, in a period of 24 hours, there was only the substitution of a chloride (Cl-) coordinated to the metal. The ligands used in substitution reactions and kinetic studies were: py, 4-pic and coordenant solvents (CH3CN and PhCN). Only the Cl- trans positioned to P of diphosphines was labilized giving rise to the entering ligand, confirming the greater trans effect of phosphine ligands in relation to N-N and N-O. The mechanism attributed to substitution reactions was dissociative because the reactions do not show dependence of ligand entry. DFT calculations showed the effective participation of the Cl atom trans to the P atom of the diphosphines in the formation of the HOMO orbital. This fact shows that the reactivity of Cl atoms is different and they can be replaced selectively. Good linearity was observed for the percentage of participation of d orbitals of ruthenium in the formation of HOMO for the dissociation of Cl- complex indicating that the strength of the Ru-Cl- bond is due to the direct interaction of the orbitals of Cl- and the d orbitals of ruthenium. Exploratory studies using irradiation of light at fixed wavelengths were performed to study possible influence of the effect of the exchange rate of Cl- and also on the isomerization reaction trans/cis-[RuCl2(dppb)(bipy)]. An increase in the rate of exchange reaction was observed in the kinetics of substitution. In the isomerization processes were not observed. The substitution reactions of Cl- in the complexes cis- [RuCl2(dppb)(N-N)] (N-N = bipy and phen) by nitrile ligands (e.g. PhCN and CH3CN), lead to the formation of complexes in which trans ligands L were coordinated by the nitrogen atom of the ligands N-N in the final complex. However, studies of 31P{1H} NMR and cyclic voltammetry confirmed that the reactions take place initially with the replacement of L trans to P atom followed by an isomerization process. This is attributed to the strong competition of π between nitrile and phosphine ligands, and its final position is determined by this effect. |
publishDate |
2010 |
dc.date.issued.fl_str_mv |
2010-10-14 |
dc.date.available.fl_str_mv |
2013-06-07 2016-06-02T20:34:42Z |
dc.date.accessioned.fl_str_mv |
2016-06-02T20:34:42Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
NASCIMENTO, Fábio Batista do. Kinetics ans Photochemical studies of Ru(II) compounds with Diimine and Diphosphine ligands of general formulae cis-[RuCl2(PP)(N-N)] (P-P = Diphosphines and N-N Bidentades N-Heterociclic ligands). 2010. 214 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/6261 |
identifier_str_mv |
NASCIMENTO, Fábio Batista do. Kinetics ans Photochemical studies of Ru(II) compounds with Diimine and Diphosphine ligands of general formulae cis-[RuCl2(PP)(N-N)] (P-P = Diphosphines and N-N Bidentades N-Heterociclic ligands). 2010. 214 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010. |
url |
https://repositorio.ufscar.br/handle/ufscar/6261 |
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por |
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por |
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e62fb48f-fa23-4158-8d60-0b17f006946c |
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info:eu-repo/semantics/openAccess |
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openAccess |
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application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos |
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Programa de Pós-Graduação em Química - PPGQ |
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UFSCar |
dc.publisher.country.fl_str_mv |
BR |
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Universidade Federal de São Carlos |
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Repositório Institucional da UFSCAR |
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