Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates

Autores
Soria, Delia Beatriz; Grundy, Joanna; Coles, Martyn P.; Hitchcock, Peter B.
Año de publicación
2005
Idioma
alemán
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Synthetic procedures to high oxidation-state complexes of niobium incorporating the bicyclic guanidinate 1,3,4,6,7,8-hexahydro-2Hpyrimido[1,2-a]pyrimidinate, [hpp]-, are described.  The ligand source was either the N-trimethylsilylated guanidine or the lithium guanidinate and the reaction proceeded via elimination of trimethylsilylchloride or transmetallation from NbCl5, respectively.  A 1 : 1 ratio of reagents afforded the mono-ligand product, Nb(hpp)Cl4 (1) and crystallization from acetonitrile afforded the solvated species Nb(hpp)Cl4(MeCN) (1a), demonstrating the ability of the metal centre in 1 to bind small substrate molecules.  A 2 : 1 ratio of lithium guanidinate to NbCl5 resulted in formation of the seven-coordinate, bis-ligand compound, Nb(hpp)2Cl3 (2).  These products represent the first examples of guanidinate compounds in which niobium is stable in the +5 oxidation-state, believed to result from enhanced electron donation caused by the bicyclic framework of the ligand.  The molecular structures of 1, 1a and 2 are reported, presenting for the first time an opportunity to describe bonding parameters within compounds of this type.
Fil: Soria, Delia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Grundy, Joanna. University of Sussex; Reino Unido
Fil: Coles, Martyn P.. University of Sussex; Reino Unido
Fil: Hitchcock, Peter B.. University of Sussex; Reino Unido
Materia
complexes of niobium
bicyclic guanidinate
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/279575
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinatesSoria, Delia BeatrizGrundy, JoannaColes, Martyn P.Hitchcock, Peter B.complexes of niobiumbicyclic guanidinatehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Synthetic procedures to high oxidation-state complexes of niobium incorporating the bicyclic guanidinate 1,3,4,6,7,8-hexahydro-2Hpyrimido[1,2-a]pyrimidinate, [hpp]-, are described.  The ligand source was either the N-trimethylsilylated guanidine or the lithium guanidinate and the reaction proceeded via elimination of trimethylsilylchloride or transmetallation from NbCl5, respectively.  A 1 : 1 ratio of reagents afforded the mono-ligand product, Nb(hpp)Cl4 (1) and crystallization from acetonitrile afforded the solvated species Nb(hpp)Cl4(MeCN) (1a), demonstrating the ability of the metal centre in 1 to bind small substrate molecules.  A 2 : 1 ratio of lithium guanidinate to NbCl5 resulted in formation of the seven-coordinate, bis-ligand compound, Nb(hpp)2Cl3 (2).  These products represent the first examples of guanidinate compounds in which niobium is stable in the +5 oxidation-state, believed to result from enhanced electron donation caused by the bicyclic framework of the ligand.  The molecular structures of 1, 1a and 2 are reported, presenting for the first time an opportunity to describe bonding parameters within compounds of this type.Fil: Soria, Delia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Grundy, Joanna. University of Sussex; Reino UnidoFil: Coles, Martyn P.. University of Sussex; Reino UnidoFil: Hitchcock, Peter B.. University of Sussex; Reino UnidoElsevier Science SA2005-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/279575Soria, Delia Beatriz; Grundy, Joanna; Coles, Martyn P.; Hitchcock, Peter B.; Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates; Elsevier Science SA; Journal of Organometallic Chemistry; 690; 9; 12-2005; 2278-22840022-328XCONICET DigitalCONICETdeuinfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022328X05001609info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jorganchem.2005.02.033info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-02-06T13:24:50Zoai:ri.conicet.gov.ar:11336/279575instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982026-02-06 13:24:51.187CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
title Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
spellingShingle Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
Soria, Delia Beatriz
complexes of niobium
bicyclic guanidinate
title_short Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
title_full Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
title_fullStr Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
title_full_unstemmed Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
title_sort Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates
dc.creator.none.fl_str_mv Soria, Delia Beatriz
Grundy, Joanna
Coles, Martyn P.
Hitchcock, Peter B.
author Soria, Delia Beatriz
author_facet Soria, Delia Beatriz
Grundy, Joanna
Coles, Martyn P.
Hitchcock, Peter B.
author_role author
author2 Grundy, Joanna
Coles, Martyn P.
Hitchcock, Peter B.
author2_role author
author
author
dc.subject.none.fl_str_mv complexes of niobium
bicyclic guanidinate
topic complexes of niobium
bicyclic guanidinate
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Synthetic procedures to high oxidation-state complexes of niobium incorporating the bicyclic guanidinate 1,3,4,6,7,8-hexahydro-2Hpyrimido[1,2-a]pyrimidinate, [hpp]-, are described.  The ligand source was either the N-trimethylsilylated guanidine or the lithium guanidinate and the reaction proceeded via elimination of trimethylsilylchloride or transmetallation from NbCl5, respectively.  A 1 : 1 ratio of reagents afforded the mono-ligand product, Nb(hpp)Cl4 (1) and crystallization from acetonitrile afforded the solvated species Nb(hpp)Cl4(MeCN) (1a), demonstrating the ability of the metal centre in 1 to bind small substrate molecules.  A 2 : 1 ratio of lithium guanidinate to NbCl5 resulted in formation of the seven-coordinate, bis-ligand compound, Nb(hpp)2Cl3 (2).  These products represent the first examples of guanidinate compounds in which niobium is stable in the +5 oxidation-state, believed to result from enhanced electron donation caused by the bicyclic framework of the ligand.  The molecular structures of 1, 1a and 2 are reported, presenting for the first time an opportunity to describe bonding parameters within compounds of this type.
Fil: Soria, Delia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Grundy, Joanna. University of Sussex; Reino Unido
Fil: Coles, Martyn P.. University of Sussex; Reino Unido
Fil: Hitchcock, Peter B.. University of Sussex; Reino Unido
description Synthetic procedures to high oxidation-state complexes of niobium incorporating the bicyclic guanidinate 1,3,4,6,7,8-hexahydro-2Hpyrimido[1,2-a]pyrimidinate, [hpp]-, are described.  The ligand source was either the N-trimethylsilylated guanidine or the lithium guanidinate and the reaction proceeded via elimination of trimethylsilylchloride or transmetallation from NbCl5, respectively.  A 1 : 1 ratio of reagents afforded the mono-ligand product, Nb(hpp)Cl4 (1) and crystallization from acetonitrile afforded the solvated species Nb(hpp)Cl4(MeCN) (1a), demonstrating the ability of the metal centre in 1 to bind small substrate molecules.  A 2 : 1 ratio of lithium guanidinate to NbCl5 resulted in formation of the seven-coordinate, bis-ligand compound, Nb(hpp)2Cl3 (2).  These products represent the first examples of guanidinate compounds in which niobium is stable in the +5 oxidation-state, believed to result from enhanced electron donation caused by the bicyclic framework of the ligand.  The molecular structures of 1, 1a and 2 are reported, presenting for the first time an opportunity to describe bonding parameters within compounds of this type.
publishDate 2005
dc.date.none.fl_str_mv 2005-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/279575
Soria, Delia Beatriz; Grundy, Joanna; Coles, Martyn P.; Hitchcock, Peter B.; Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates; Elsevier Science SA; Journal of Organometallic Chemistry; 690; 9; 12-2005; 2278-2284
0022-328X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/279575
identifier_str_mv Soria, Delia Beatriz; Grundy, Joanna; Coles, Martyn P.; Hitchcock, Peter B.; Stabilisation of high oxidation-state niobium using ‘electron-rich’ bicyclic-guanidinates; Elsevier Science SA; Journal of Organometallic Chemistry; 690; 9; 12-2005; 2278-2284
0022-328X
CONICET Digital
CONICET
dc.language.none.fl_str_mv deu
language deu
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022328X05001609
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jorganchem.2005.02.033
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science SA
publisher.none.fl_str_mv Elsevier Science SA
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.106097

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