Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction

The novel nitrosyl-bridged complex [W2Cp2(μ-PtBu2)(μ-κ:η-NO)(CO)(NO)](BAr4) [Ar = 3,5-C6H3(CF3)2] was prepared in a multistep procedure starting from the hydride [W2Cp2(μ-H)(μ-PtBu2)(CO)4] and involving the new complexes [W2Cp2(μ-PtBu2)(CO)4](BF4), [W2Cp2(μ-PtBu2)(CO)2(NO)2](BAr4), and [W2(μ-κ:η5-C5...

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Autores: Alvarez, M. Angeles, García, M. Esther, García-Vivó, Daniel, Guerra, Ana M., Ruiz, Miguel A., Falvello, Larry R.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/287806
Acceso en línea:http://hdl.handle.net/10261/287806
Access Level:acceso abierto
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spelling Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reactionAlvarez, M. AngelesGarcía, M. EstherGarcía-Vivó, DanielGuerra, Ana M.Ruiz, Miguel A.Falvello, Larry R.The novel nitrosyl-bridged complex [W2Cp2(μ-PtBu2)(μ-κ:η-NO)(CO)(NO)](BAr4) [Ar = 3,5-C6H3(CF3)2] was prepared in a multistep procedure starting from the hydride [W2Cp2(μ-H)(μ-PtBu2)(CO)4] and involving the new complexes [W2Cp2(μ-PtBu2)(CO)4](BF4), [W2Cp2(μ-PtBu2)(CO)2(NO)2](BAr4), and [W2(μ-κ:η5-C5H4)Cp(μ-PtBu2)(CO)(NO)2] as intermediates, which follow from reactions with HBF4·OEt2, NO, and Me3NO·2H2O, respectively. The nitrosyl-bridged cation easily added chloride upon reaction with [N(PPh3)2]Cl, with concomitant NO rearrangement into the terminal coordination mode, to give [W2ClCp2(μ-PtBu2)(CO)(NO)2], and underwent N–O and W–W bond cleavages upon the addition of CNtBu to give the mononuclear phosphinoimido complex [WCp(NPtBu2)(CNtBu)2](BAr4). Another N–O bond cleavage was induced upon photochemical decarbonylation at 243 K, which gave the oxo- and phosphinito-bridged nitrido complex [W2Cp2(N)(μ-O)(μ-OPtBu2)(NO)](BAr4), likely resulting from a N–O bond cleavage step following decarbonylation.We thank the MICINN of Spain and FEDER for financial support (Projects PGC2018-097366-B-I00 and -PGC2018-093451B-I00).Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia, Innovación y Universidades (España)European CommissionAgencia Estatal de Investigación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202320232022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/287806reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-097366-B-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-093451-B-I00Inorganic Chemistryhttps://doi.org/10.1021/acs.inorgchem.2c02216Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2878062026-05-22T06:33:51Z
dc.title.none.fl_str_mv Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
title Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
spellingShingle Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
Alvarez, M. Angeles
title_short Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
title_full Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
title_fullStr Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
title_full_unstemmed Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
title_sort Chemistry of a nitrosyl ligand κ:η-bridging a ditungsten center: Rearrangement and N-O bond cleavage reaction
dc.creator.none.fl_str_mv Alvarez, M. Angeles
García, M. Esther
García-Vivó, Daniel
Guerra, Ana M.
Ruiz, Miguel A.
Falvello, Larry R.
author Alvarez, M. Angeles
author_facet Alvarez, M. Angeles
García, M. Esther
García-Vivó, Daniel
Guerra, Ana M.
Ruiz, Miguel A.
Falvello, Larry R.
author_role author
author2 García, M. Esther
García-Vivó, Daniel
Guerra, Ana M.
Ruiz, Miguel A.
Falvello, Larry R.
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
European Commission
Agencia Estatal de Investigación (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The novel nitrosyl-bridged complex [W2Cp2(μ-PtBu2)(μ-κ:η-NO)(CO)(NO)](BAr4) [Ar = 3,5-C6H3(CF3)2] was prepared in a multistep procedure starting from the hydride [W2Cp2(μ-H)(μ-PtBu2)(CO)4] and involving the new complexes [W2Cp2(μ-PtBu2)(CO)4](BF4), [W2Cp2(μ-PtBu2)(CO)2(NO)2](BAr4), and [W2(μ-κ:η5-C5H4)Cp(μ-PtBu2)(CO)(NO)2] as intermediates, which follow from reactions with HBF4·OEt2, NO, and Me3NO·2H2O, respectively. The nitrosyl-bridged cation easily added chloride upon reaction with [N(PPh3)2]Cl, with concomitant NO rearrangement into the terminal coordination mode, to give [W2ClCp2(μ-PtBu2)(CO)(NO)2], and underwent N–O and W–W bond cleavages upon the addition of CNtBu to give the mononuclear phosphinoimido complex [WCp(NPtBu2)(CNtBu)2](BAr4). Another N–O bond cleavage was induced upon photochemical decarbonylation at 243 K, which gave the oxo- and phosphinito-bridged nitrido complex [W2Cp2(N)(μ-O)(μ-OPtBu2)(NO)](BAr4), likely resulting from a N–O bond cleavage step following decarbonylation.
publishDate 2022
dc.date.none.fl_str_mv 2022
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/287806
url http://hdl.handle.net/10261/287806
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-097366-B-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-093451-B-I00
Inorganic Chemistry
https://doi.org/10.1021/acs.inorgchem.2c02216
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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