From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands

Different coordination modes of a PGeP chloridogermyl ligand (Ge,P-chelating and P,Ge,P-tripodal) and a PGeP germylene ligand (P,Ge,P-bridging and Ge,P-chelating) have been identified in coordination compounds resulting from reactions of the PGeP pincer-type diphosphane-germylene Ge(NCH2PtBu2)2C6H4...

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Autores: Brugos, Javier, Cabeza, Javier A., García-Álvarez, Pablo, Pérez-Carreño, Enrique
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/359591
Acceso en línea:http://hdl.handle.net/10261/359591
Access Level:acceso abierto
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spelling From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligandsBrugos, JavierCabeza, Javier A.García-Álvarez, PabloPérez-Carreño, EnriqueDifferent coordination modes of a PGeP chloridogermyl ligand (Ge,P-chelating and P,Ge,P-tripodal) and a PGeP germylene ligand (P,Ge,P-bridging and Ge,P-chelating) have been identified in coordination compounds resulting from reactions of the PGeP pincer-type diphosphane-germylene Ge(NCH2PtBu2)2C6H4 (1) with iridium(I), manganese(0), and ruthenium(II) complex reagents. Germylene 1 reacted with [Ir2(μ-Cl)2(η4-cod)2] (cod = 1,5-cyclooctadiene) to give [Ir{κ2Ge,P-GeCl(NCH2PtBu2)2C6H4}(η4-cod)] (2), which contains a Ge,P-chelating PGeP chloridogermyl ligand and an uncoordinated phosphane group that weakly interacts with the Ge atom. Carbon monoxide readily displaced the cod ligand of 2 to give the dicarbonyl derivative [Ir{κ3P,Ge,P-GeCl(NCH2PtBu2)2C6H4}(CO)2] (3), in which the PGeP chloridogermyl ligand displays a P,Ge,P-tripodal coordination mode. A bridging germylene moiety has been identified in the binuclear derivative [Mn2{μ-κ3P,Ge,P-Ge(NCH2PtBu2)2C6H4}(CO)8] (4), which resulted from the treatment of [Mn2(CO)10] with germylene 1. The ruthenium complex [RuHCl(CO){κ2Ge,P-Ge(NCH2PtBu2)2C6H4}(PiPr3)] (5), which was isolated from the reaction of 1 with [RuHCl(CO)(PiPr3)2], is the first transition-metal derivative of 1 in which the germylene moiety has not inserted into an M–M or M–Cl bond (M = transition metal), as it contains germylene 1 coordinated in a Ge,P-chelating mode, the resulting GeNCPRu ring being severely strained due to the short length of the coordinated CH2PtBu2 arm, which also forces the germanium atom to be in an uncommon T-shaped environment. DFT calculations have been used to shed light on bonding features of complexes 2 and 5. The X-ray structures of 1–5 are also reported.This work has been supported by MINECO-FEDER (CTQ2016-75218-P, MAT2016-78155-C2-1-R, RYC2012-10491, and CTQ2016-81797-REDC) and Gobierno del Principado de Asturias (GRUPIN14-009 and GRUPIN14-060) research grants.Peer reviewedAmerican Chemical SocietyMinisterio de Economía y Competitividad (España)European CommissionPrincipado de Asturias202420242018info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://hdl.handle.net/10261/359591reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO//CTQ2016-75218-Pinfo:eu-repo/grantAgreement/MINECO//MAT2016-78155-C2-1-Rinfo:eu-repo/grantAgreement/MINECO//CTQ2016-81797-REDCBrugos, Javier; Cabeza, Javier A.; García-Álvarez, Pablo; Pérez-Carreño, Enrique; 2018; Supporting Information: From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.organomet.8b00171https://doi.org/10.1021/acs.organomet.8b00171Noinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3595912026-05-22T06:33:51Z
dc.title.none.fl_str_mv From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
title From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
spellingShingle From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
Brugos, Javier
title_short From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
title_full From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
title_fullStr From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
title_full_unstemmed From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
title_sort From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands
dc.creator.none.fl_str_mv Brugos, Javier
Cabeza, Javier A.
García-Álvarez, Pablo
Pérez-Carreño, Enrique
author Brugos, Javier
author_facet Brugos, Javier
Cabeza, Javier A.
García-Álvarez, Pablo
Pérez-Carreño, Enrique
author_role author
author2 Cabeza, Javier A.
García-Álvarez, Pablo
Pérez-Carreño, Enrique
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
European Commission
Principado de Asturias
description Different coordination modes of a PGeP chloridogermyl ligand (Ge,P-chelating and P,Ge,P-tripodal) and a PGeP germylene ligand (P,Ge,P-bridging and Ge,P-chelating) have been identified in coordination compounds resulting from reactions of the PGeP pincer-type diphosphane-germylene Ge(NCH2PtBu2)2C6H4 (1) with iridium(I), manganese(0), and ruthenium(II) complex reagents. Germylene 1 reacted with [Ir2(μ-Cl)2(η4-cod)2] (cod = 1,5-cyclooctadiene) to give [Ir{κ2Ge,P-GeCl(NCH2PtBu2)2C6H4}(η4-cod)] (2), which contains a Ge,P-chelating PGeP chloridogermyl ligand and an uncoordinated phosphane group that weakly interacts with the Ge atom. Carbon monoxide readily displaced the cod ligand of 2 to give the dicarbonyl derivative [Ir{κ3P,Ge,P-GeCl(NCH2PtBu2)2C6H4}(CO)2] (3), in which the PGeP chloridogermyl ligand displays a P,Ge,P-tripodal coordination mode. A bridging germylene moiety has been identified in the binuclear derivative [Mn2{μ-κ3P,Ge,P-Ge(NCH2PtBu2)2C6H4}(CO)8] (4), which resulted from the treatment of [Mn2(CO)10] with germylene 1. The ruthenium complex [RuHCl(CO){κ2Ge,P-Ge(NCH2PtBu2)2C6H4}(PiPr3)] (5), which was isolated from the reaction of 1 with [RuHCl(CO)(PiPr3)2], is the first transition-metal derivative of 1 in which the germylene moiety has not inserted into an M–M or M–Cl bond (M = transition metal), as it contains germylene 1 coordinated in a Ge,P-chelating mode, the resulting GeNCPRu ring being severely strained due to the short length of the coordinated CH2PtBu2 arm, which also forces the germanium atom to be in an uncommon T-shaped environment. DFT calculations have been used to shed light on bonding features of complexes 2 and 5. The X-ray structures of 1–5 are also reported.
publishDate 2018
dc.date.none.fl_str_mv 2018
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/359591
url http://hdl.handle.net/10261/359591
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/MINECO//CTQ2016-75218-P
info:eu-repo/grantAgreement/MINECO//MAT2016-78155-C2-1-R
info:eu-repo/grantAgreement/MINECO//CTQ2016-81797-REDC
Brugos, Javier; Cabeza, Javier A.; García-Álvarez, Pablo; Pérez-Carreño, Enrique; 2018; Supporting Information: From a PGeP pincer-type germylene to metal complexes featuring chelating (Ir) and tripodal (Ir) PGeP germyl and bridging (Mn2) and chelating (Ru) PGeP germylene ligands [Dataset]; American Chemical Society; https://doi.org/10.1021/acs.organomet.8b00171
https://doi.org/10.1021/acs.organomet.8b00171
No
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
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