Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study

Unprecedented metallapyrazoles [IrH2{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (3) and [IrHCl{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (4) were obtained by the reaction of the irida-β-ketoimine [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNH2))H}] (2) in MeOH heated at reflux in the presence and absence of KOH, respectively....

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Autores: Zumeta Subijana, Itziar, Mendicute Fierro, Claudio, Bustos Rosas, Itxaso, Huertos Mansilla, Miguel Angel, Rodríguez Diéguez, Antonio, Seco Botana, José Manuel, San Sebastián Larzabal, Eider, Garralda Hualde, María Angeles
Tipo de recurso: artículo
Fecha de publicación:2016
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/64381
Acceso en línea:http://hdl.handle.net/10810/64381
Access Level:acceso abierto
Palabra clave:iridacycle
hydrazine
metallapyrazole
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spelling Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental StudyZumeta Subijana, ItziarMendicute Fierro, ClaudioBustos Rosas, ItxasoHuertos Mansilla, Miguel AngelRodríguez Diéguez, AntonioSeco Botana, José ManuelSan Sebastián Larzabal, EiderGarralda Hualde, María AngelesiridacyclehydrazinemetallapyrazoleUnprecedented metallapyrazoles [IrH2{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (3) and [IrHCl{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (4) were obtained by the reaction of the irida-β-ketoimine [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNH2))H}] (2) in MeOH heated at reflux in the presence and absence of KOH, respectively. In solution, iridapyrazole 3 undergoes a dynamic process due to prototropic tautomerism with an experimental barrier for the exchange of ΔGcoal⧧ = 53.7 kJ mol–1. DFT calculations agreed with an intrapyrazole proton transfer process assisted by two water molecules (ΔG = 63.1 kJ mol–1). An X-ray diffraction study on 4 indicated electron delocalization in the iridapyrazole ring. The reaction of the irida-β-diketone [IrHCl{(PPh2(o-C6H4CO))2H}] (1) with H2NNRR′ in aprotic solvents gave irida-β-ketoimines [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNRR′))H}] (R = R′ = Me (5); R = H, R′ = Ph (8)), which can undergo N–N bond cleavage to afford the acyl–amide complex [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4C(O)N(CH3)2))-κP,κO] (6) or [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CN)-κP)(NH2NHPh-κNH2)] (9) containing o-(diphenylphosphine)benzonitrile and phenylhydrazine, respectively. From a CH2Cl2/CH3OH solution of 9 kept at −18 °C, single crystals of [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CN)-κP))(HN═NPh-κNH)] (10) containing o-(diphenylphosphine)benzonitrile and phenyldiazene were formed, as shown by X-ray diffraction. The reaction of 1 with methylhydrazine in methanol gave the hydrazine complex [IrCl(PPh2(o-C6H4CO))2(NH2NH(CH3)-κNH2)] (7). Single-crystal X-ray diffraction analysis was performed on 6 and 7.Partial financial support by Ministerio de Economía y Competitividad (CTQ2015-65268-C2-1-P and CTQ2015-65268-C2-2-P), Gobierno Vasco (S-PE13UN023), and Universidad del País Vasco (UPV/EHU) (GIU 13/06) is gratefully acknowledged. I.Z. is grateful to Gobierno Vasco for a scholarship. Technical and human support provided by IZO-SGI, SGIker (UPV/EHU, MICINN, GV/EJ, ERDF, and ESF) is gratefully acknowledged.ACS202420242016info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/64381reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MINECO/CTQ2015-65268-C2-1-P/info:eu-repo/grantAgreement/MINECO/CTQ2015-65268-C2-2-P/https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b01550info:eu-repo/semantics/openAccess© 2016 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permitscopying and redistribution of the article or any adaptations for non-commercial purposes.oai:addi.ehu.eus:10810/643812026-06-18T09:23:17Z
dc.title.none.fl_str_mv Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
title Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
spellingShingle Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
Zumeta Subijana, Itziar
iridacycle
hydrazine
metallapyrazole
title_short Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
title_full Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
title_fullStr Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
title_full_unstemmed Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
title_sort Irida-β-ketoimines derived from Hydrazines to Afford Metallapyrazoles or N-N Bond Cleavage: A Missing Metallacycle Disclosed by a Theoretical and Experimental Study
dc.creator.none.fl_str_mv Zumeta Subijana, Itziar
Mendicute Fierro, Claudio
Bustos Rosas, Itxaso
Huertos Mansilla, Miguel Angel
Rodríguez Diéguez, Antonio
Seco Botana, José Manuel
San Sebastián Larzabal, Eider
Garralda Hualde, María Angeles
author Zumeta Subijana, Itziar
author_facet Zumeta Subijana, Itziar
Mendicute Fierro, Claudio
Bustos Rosas, Itxaso
Huertos Mansilla, Miguel Angel
Rodríguez Diéguez, Antonio
Seco Botana, José Manuel
San Sebastián Larzabal, Eider
Garralda Hualde, María Angeles
author_role author
author2 Mendicute Fierro, Claudio
Bustos Rosas, Itxaso
Huertos Mansilla, Miguel Angel
Rodríguez Diéguez, Antonio
Seco Botana, José Manuel
San Sebastián Larzabal, Eider
Garralda Hualde, María Angeles
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv iridacycle
hydrazine
metallapyrazole
topic iridacycle
hydrazine
metallapyrazole
description Unprecedented metallapyrazoles [IrH2{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (3) and [IrHCl{Ph2P(o-C6H4)CNNHC(o-C6H4)PPh2}] (4) were obtained by the reaction of the irida-β-ketoimine [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNH2))H}] (2) in MeOH heated at reflux in the presence and absence of KOH, respectively. In solution, iridapyrazole 3 undergoes a dynamic process due to prototropic tautomerism with an experimental barrier for the exchange of ΔGcoal⧧ = 53.7 kJ mol–1. DFT calculations agreed with an intrapyrazole proton transfer process assisted by two water molecules (ΔG = 63.1 kJ mol–1). An X-ray diffraction study on 4 indicated electron delocalization in the iridapyrazole ring. The reaction of the irida-β-diketone [IrHCl{(PPh2(o-C6H4CO))2H}] (1) with H2NNRR′ in aprotic solvents gave irida-β-ketoimines [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CNNRR′))H}] (R = R′ = Me (5); R = H, R′ = Ph (8)), which can undergo N–N bond cleavage to afford the acyl–amide complex [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4C(O)N(CH3)2))-κP,κO] (6) or [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CN)-κP)(NH2NHPh-κNH2)] (9) containing o-(diphenylphosphine)benzonitrile and phenylhydrazine, respectively. From a CH2Cl2/CH3OH solution of 9 kept at −18 °C, single crystals of [IrHCl(PPh2(o-C6H4CO))(PPh2(o-C6H4CN)-κP))(HN═NPh-κNH)] (10) containing o-(diphenylphosphine)benzonitrile and phenyldiazene were formed, as shown by X-ray diffraction. The reaction of 1 with methylhydrazine in methanol gave the hydrazine complex [IrCl(PPh2(o-C6H4CO))2(NH2NH(CH3)-κNH2)] (7). Single-crystal X-ray diffraction analysis was performed on 6 and 7.
publishDate 2016
dc.date.none.fl_str_mv 2016
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/64381
url http://hdl.handle.net/10810/64381
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MINECO/CTQ2015-65268-C2-1-P/
info:eu-repo/grantAgreement/MINECO/CTQ2015-65268-C2-2-P/
https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b01550
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
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instname_str Universidad del País Vasco
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collection Addi. Archivo Digital para la Docencia y la Investigación
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