Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies
Autor(a) principal: | |
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Data de Publicação: | 2016 |
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/10400.21/7148 |
Resumo: | Treatment of trans-[Mo(NCN)(2)(dppe)(2)] with alkyl halides (RX) affords the alkylated cyanoimidocomplexes trans-[Mo(NCN)(NCNR)(dppe)(2)]X [R = Me, X = I (1); R = Et, X = I (2); R = Pr, X = I (3); R = Pr-i, X = I (4); R = CH2Ph, X = Br (5); R = CH2C6H4NO2-4, X = Br (6)], while its reaction with the trimethyloxonium salt [Me3O][BF4] affords trans-[Mo(NCN)(NCNMe)(dppe)(2)][BF4] (7). The reactions are accelerated by microwave irradiation. Complexes 1-7 were fully characterized by elemental analyses, IR and NMR spectroscopies, FAB-MS spectrometry, cyclic voltammetry and controlled potential electrolysis. The electrophilic addition to the exo-N atom of one of the cyanoimide ligands was confirmed by single crystal X-ray crystal analysis of 1. In aprotic medium and at a Pt electrode, compounds 1-7 undergo, apart from two consecutive single-electron reversible oxidations, also two successive single-electron reductions at different potentials, involving a cathodically induced trans-to-cis isomerization, following a double square ECEC-type mechanism which was studied in detail by digital simulation of the cyclic voltammograms. Quantum-chemical calculations indicate that the oxidations and reductions are mainly metal centered (although the latter with some involvement of the cyanoimide moieties), and that the reduction leads to a decrease of the relative stability of the trans isomer vs. the cis one. |
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Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studiesCyanoimido complexesAlkylated cyanoimidoDigital simulation of cyclic voltammetryElectron-transfer induced reactionsDouble square ECEC-type mechanismTreatment of trans-[Mo(NCN)(2)(dppe)(2)] with alkyl halides (RX) affords the alkylated cyanoimidocomplexes trans-[Mo(NCN)(NCNR)(dppe)(2)]X [R = Me, X = I (1); R = Et, X = I (2); R = Pr, X = I (3); R = Pr-i, X = I (4); R = CH2Ph, X = Br (5); R = CH2C6H4NO2-4, X = Br (6)], while its reaction with the trimethyloxonium salt [Me3O][BF4] affords trans-[Mo(NCN)(NCNMe)(dppe)(2)][BF4] (7). The reactions are accelerated by microwave irradiation. Complexes 1-7 were fully characterized by elemental analyses, IR and NMR spectroscopies, FAB-MS spectrometry, cyclic voltammetry and controlled potential electrolysis. The electrophilic addition to the exo-N atom of one of the cyanoimide ligands was confirmed by single crystal X-ray crystal analysis of 1. In aprotic medium and at a Pt electrode, compounds 1-7 undergo, apart from two consecutive single-electron reversible oxidations, also two successive single-electron reductions at different potentials, involving a cathodically induced trans-to-cis isomerization, following a double square ECEC-type mechanism which was studied in detail by digital simulation of the cyclic voltammograms. Quantum-chemical calculations indicate that the oxidations and reductions are mainly metal centered (although the latter with some involvement of the cyanoimide moieties), and that the reduction leads to a decrease of the relative stability of the trans isomer vs. the cis one.ElsevierRCIPLAlegria, ElisabeteGuedes Da Silva, M. Fátima C.Kuznetsov, Maxim L.Martins, LuisaPombeiro, Armando2017-06-05T12:00:33Z2016-112016-11-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/7148engALEGRIA, Elisabete C. B. A. [et al] - Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies. Electrochimica Acta. ISSN: 0013-4686. Vol. 218 (2016), pp. 252-262.0013-468610.1016/j.electacta.2016.09.120metadata 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:RCAAP2023-08-03T09:52:50Zoai:repositorio.ipl.pt:10400.21/7148Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:16:09.459992Repositório 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 |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies |
title |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies |
spellingShingle |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies Alegria, Elisabete Cyanoimido complexes Alkylated cyanoimido Digital simulation of cyclic voltammetry Electron-transfer induced reactions Double square ECEC-type mechanism |
title_short |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies |
title_full |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies |
title_fullStr |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies |
title_full_unstemmed |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies |
title_sort |
Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies |
author |
Alegria, Elisabete |
author_facet |
Alegria, Elisabete Guedes Da Silva, M. Fátima C. Kuznetsov, Maxim L. Martins, Luisa Pombeiro, Armando |
author_role |
author |
author2 |
Guedes Da Silva, M. Fátima C. Kuznetsov, Maxim L. Martins, Luisa Pombeiro, Armando |
author2_role |
author author author author |
dc.contributor.none.fl_str_mv |
RCIPL |
dc.contributor.author.fl_str_mv |
Alegria, Elisabete Guedes Da Silva, M. Fátima C. Kuznetsov, Maxim L. Martins, Luisa Pombeiro, Armando |
dc.subject.por.fl_str_mv |
Cyanoimido complexes Alkylated cyanoimido Digital simulation of cyclic voltammetry Electron-transfer induced reactions Double square ECEC-type mechanism |
topic |
Cyanoimido complexes Alkylated cyanoimido Digital simulation of cyclic voltammetry Electron-transfer induced reactions Double square ECEC-type mechanism |
description |
Treatment of trans-[Mo(NCN)(2)(dppe)(2)] with alkyl halides (RX) affords the alkylated cyanoimidocomplexes trans-[Mo(NCN)(NCNR)(dppe)(2)]X [R = Me, X = I (1); R = Et, X = I (2); R = Pr, X = I (3); R = Pr-i, X = I (4); R = CH2Ph, X = Br (5); R = CH2C6H4NO2-4, X = Br (6)], while its reaction with the trimethyloxonium salt [Me3O][BF4] affords trans-[Mo(NCN)(NCNMe)(dppe)(2)][BF4] (7). The reactions are accelerated by microwave irradiation. Complexes 1-7 were fully characterized by elemental analyses, IR and NMR spectroscopies, FAB-MS spectrometry, cyclic voltammetry and controlled potential electrolysis. The electrophilic addition to the exo-N atom of one of the cyanoimide ligands was confirmed by single crystal X-ray crystal analysis of 1. In aprotic medium and at a Pt electrode, compounds 1-7 undergo, apart from two consecutive single-electron reversible oxidations, also two successive single-electron reductions at different potentials, involving a cathodically induced trans-to-cis isomerization, following a double square ECEC-type mechanism which was studied in detail by digital simulation of the cyclic voltammograms. Quantum-chemical calculations indicate that the oxidations and reductions are mainly metal centered (although the latter with some involvement of the cyanoimide moieties), and that the reduction leads to a decrease of the relative stability of the trans isomer vs. the cis one. |
publishDate |
2016 |
dc.date.none.fl_str_mv |
2016-11 2016-11-01T00:00:00Z 2017-06-05T12:00:33Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10400.21/7148 |
url |
http://hdl.handle.net/10400.21/7148 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
ALEGRIA, Elisabete C. B. A. [et al] - Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies. Electrochimica Acta. ISSN: 0013-4686. Vol. 218 (2016), pp. 252-262. 0013-4686 10.1016/j.electacta.2016.09.120 |
dc.rights.driver.fl_str_mv |
metadata only access info:eu-repo/semantics/openAccess |
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metadata only access |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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