Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions

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:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:119908
Acceso en línea:http://zaguan.unizar.es/record/119908
Access Level:acceso abierto
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spelling Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactionsAlvarez, 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.2022info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/119908reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-093451-B-I00info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-097366-B-I00info:eu-repo/semantics/openAccessoai:zaguan.unizar.es:1199082026-05-29T13:59:51Z
dc.title.none.fl_str_mv Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
title Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
spellingShingle Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
Alvarez, M. Angeles
title_short Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
title_full Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
title_fullStr Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
title_full_unstemmed Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
title_sort Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions
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
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
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/119908
url http://zaguan.unizar.es/record/119908
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-093451-B-I00
info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-097366-B-I00
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
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
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