Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity

The iridium complex 1 based on a metalated CNP ligand containing an imidazolin-2-ylidene fragment has been prepared by treatment of the ligand precursor 4 with Ag2O followed by reaction with [IrCl(COE)2]2. The chlorohydride imidazolidin-2-ylidene complex 6, which is isostructural to 1, was synthetiz...

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Autores: Hernández Juárez, Martín, Sánchez, Práxedes, López Serrano, Joaquín, Lara Muñoz, Patricia, González Herrero, Pablo, Rendón Márquez, Nuria, Álvarez, Eleuterio, Paneque, Margarita, Suárez, Andrés
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Recursos:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/143144
Acesso em linha:https://hdl.handle.net/11441/143144
https://doi.org/10.1002/ejic.202000681
Access Level:acceso abierto
Palavra-chave:Carbene ligands
Hydrogenation
Ligand design
Luminescence
Proton-responsive ligands
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spelling Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative ReactivityHernández Juárez, MartínSánchez, PráxedesLópez Serrano, JoaquínLara Muñoz, PatriciaGonzález Herrero, PabloRendón Márquez, NuriaÁlvarez, EleuterioPaneque, MargaritaSuárez, AndrésCarbene ligandsHydrogenationLigand designLuminescenceProton-responsive ligandsThe iridium complex 1 based on a metalated CNP ligand containing an imidazolin-2-ylidene fragment has been prepared by treatment of the ligand precursor 4 with Ag2O followed by reaction with [IrCl(COE)2]2. The chlorohydride imidazolidin-2-ylidene complex 6, which is isostructural to 1, was synthetized by reaction of the previously reported dihydride derivative 3 with CH2Cl2. Complexes 1 and 6 exhibit luminescence arising from a 3MLCT/ILCT state involving the metalated CNP ligand, which is particularly intense for 1 in the solid state at 298 K. Furthermore, the reactivity of complexes 1 and 6 towards bases was compared. Deprotonation of 1 with KOtBu produced the selective formation of the dinuclear complex 7; meanwhile, the reaction of 6 led to a complex mixture of products. The same reactions carried out in the presence of PPh3 produced the selective deprotonation of the P-bonded methylene bridges of 1 and 6, yielding the isostructural derivatives 9 and 10. DFT calculations performed on the uNHC-containing tautomers I and II, and the sNHC-based isomers III and IV, showed that the NHC-deprotonated derivatives II and IV are more stable by 3.20 and 2.73 kcal mol–1, respectively, than their P-deprotonated counterparts (I and III). However, a reverse stability order was observed for hexacoordinated tautomers I·L and II·L, and III·L and IV·L (L = PPh3, CO, MeCN). Finally, the catalytic activity of complex 3 in the transfer hydrogenation of ketones has been assessed.Ministerio de Ciencia, Innovación y Universidades CTQ2015-69568-P, CTQ2016-75193-P, CTQ2016-80814-R, CTQ2016-81797-REDCFundación Séneca 19890/GERM/15Junta de Andalucía PY18-3208Consejo Nacional de Ciencia y Tecnología 263719Wiley-BlackwellQuímica InorgánicaMinisterio de Ciencia, Innovación y Universidades (MICINN). EspañaFundación SénecaJunta de AndalucíaConsejo Nacional de Ciencia y Tecnología (CONACYT). México2020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/143144https://doi.org/10.1002/ejic.202000681reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésEuropean Journal of Inorganic Chemistry, 2020 (41), 3944-3953.CTQ2015-69568-PCTQ2016-75193-PCTQ2016-80814-RCTQ2016-81797-REDC19890/GERM/15PY18-3208263719https://dx.doi.org/10.1002/ejic.202000681info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1431442026-06-17T12:51:07Z
dc.title.none.fl_str_mv Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
title Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
spellingShingle Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
Hernández Juárez, Martín
Carbene ligands
Hydrogenation
Ligand design
Luminescence
Proton-responsive ligands
title_short Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
title_full Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
title_fullStr Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
title_full_unstemmed Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
title_sort Metalated Ir–CNP Complexes Containing Imidazolin-2-ylidene and Imidazolidin-2-ylidene Donors – Synthesis, Structure, Luminescence, and Metal–Ligand Cooperative Reactivity
dc.creator.none.fl_str_mv Hernández Juárez, Martín
Sánchez, Práxedes
López Serrano, Joaquín
Lara Muñoz, Patricia
González Herrero, Pablo
Rendón Márquez, Nuria
Álvarez, Eleuterio
Paneque, Margarita
Suárez, Andrés
author Hernández Juárez, Martín
author_facet Hernández Juárez, Martín
Sánchez, Práxedes
López Serrano, Joaquín
Lara Muñoz, Patricia
González Herrero, Pablo
Rendón Márquez, Nuria
Álvarez, Eleuterio
Paneque, Margarita
Suárez, Andrés
author_role author
author2 Sánchez, Práxedes
López Serrano, Joaquín
Lara Muñoz, Patricia
González Herrero, Pablo
Rendón Márquez, Nuria
Álvarez, Eleuterio
Paneque, Margarita
Suárez, Andrés
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Química Inorgánica
Ministerio de Ciencia, Innovación y Universidades (MICINN). España
Fundación Séneca
Junta de Andalucía
Consejo Nacional de Ciencia y Tecnología (CONACYT). México
dc.subject.none.fl_str_mv Carbene ligands
Hydrogenation
Ligand design
Luminescence
Proton-responsive ligands
topic Carbene ligands
Hydrogenation
Ligand design
Luminescence
Proton-responsive ligands
description The iridium complex 1 based on a metalated CNP ligand containing an imidazolin-2-ylidene fragment has been prepared by treatment of the ligand precursor 4 with Ag2O followed by reaction with [IrCl(COE)2]2. The chlorohydride imidazolidin-2-ylidene complex 6, which is isostructural to 1, was synthetized by reaction of the previously reported dihydride derivative 3 with CH2Cl2. Complexes 1 and 6 exhibit luminescence arising from a 3MLCT/ILCT state involving the metalated CNP ligand, which is particularly intense for 1 in the solid state at 298 K. Furthermore, the reactivity of complexes 1 and 6 towards bases was compared. Deprotonation of 1 with KOtBu produced the selective formation of the dinuclear complex 7; meanwhile, the reaction of 6 led to a complex mixture of products. The same reactions carried out in the presence of PPh3 produced the selective deprotonation of the P-bonded methylene bridges of 1 and 6, yielding the isostructural derivatives 9 and 10. DFT calculations performed on the uNHC-containing tautomers I and II, and the sNHC-based isomers III and IV, showed that the NHC-deprotonated derivatives II and IV are more stable by 3.20 and 2.73 kcal mol–1, respectively, than their P-deprotonated counterparts (I and III). However, a reverse stability order was observed for hexacoordinated tautomers I·L and II·L, and III·L and IV·L (L = PPh3, CO, MeCN). Finally, the catalytic activity of complex 3 in the transfer hydrogenation of ketones has been assessed.
publishDate 2020
dc.date.none.fl_str_mv 2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/143144
https://doi.org/10.1002/ejic.202000681
url https://hdl.handle.net/11441/143144
https://doi.org/10.1002/ejic.202000681
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv European Journal of Inorganic Chemistry, 2020 (41), 3944-3953.
CTQ2015-69568-P
CTQ2016-75193-P
CTQ2016-80814-R
CTQ2016-81797-REDC
19890/GERM/15
PY18-3208
263719
https://dx.doi.org/10.1002/ejic.202000681
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley-Blackwell
publisher.none.fl_str_mv Wiley-Blackwell
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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