Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations

Autores
Pérez Pérez, Hiram; Gil, Diego Mauricio; Gomila, Rosa M.; Frontera, Antonio
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The crystal structures of seven metal dihalide complexes with triphenylphosphine (PPh₃) and two with tribenzylphosphine (PBz₃) have been reanalyzed. The studied complexes include [FeCl₂(PPh₃)₂], [CoCl₂(PPh₃)₂], [CoBr₂(PPh₃)₂], [NiCl₂(PPh₃)₂], [NiBr₂(PPh₃)₂], [NiI₂(PPh₃)₂], [ZnCl₂(PPh₃)₂], [NiCl₂(PBz₃)₂], and [NiBr₂(PBz₃)₂]. A detailed geometric analysis revealed high isostructurality among several pairs. Ligand steric effects were assessed using cone angles and percentage surface coverage. Crystal packing is stabilized by weak C─H⋯π and C─H⋯X (X = Cl, Br, and I) interactions. Notably, [NiCl₂(PBz₃)₂] and [NiBr₂(PBz₃)₂] feature rare intramolecular C─H⋯Ni anagostic interactions. Reduced density gradient (RDG) and noncovalent interaction (NCI) plots confirmed weakly attractive C─H⋯π contacts in all complexes. Void-volume analysis assessed the mechanical strength of the crystals, while pixel energy and energy frameworks clarified structural stability and dominant interactions. Density Functional Theory (DFT) calculations, along with QTAIM/NCIplot and NBO analyses, as well as electron density (ED) versus electrostatic potential (ESP) plots, were performed to better understand the C─H···Ni interactions and distinguish between agostic and anagostic interactions.
Fil: Pérez Pérez, Hiram. Universidad de La Habana; Cuba
Fil: Gil, Diego Mauricio. Universidad Nacional de Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Orgánica; Argentina
Fil: Gomila, Rosa M.. Universidad de las Islas Baleares; España
Fil: Frontera, Antonio. Universidad de las Islas Baleares; España
Materia
ANAGOSTIC INTERACTION
CRYSTAL VOIDS ENERGY
ISOSTRUCTURALITY
PHOSPINES
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/262786
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/262786
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic CalculationsPérez Pérez, HiramGil, Diego MauricioGomila, Rosa M.Frontera, AntonioANAGOSTIC INTERACTIONCRYSTAL VOIDS ENERGYISOSTRUCTURALITYPHOSPINEShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The crystal structures of seven metal dihalide complexes with triphenylphosphine (PPh₃) and two with tribenzylphosphine (PBz₃) have been reanalyzed. The studied complexes include [FeCl₂(PPh₃)₂], [CoCl₂(PPh₃)₂], [CoBr₂(PPh₃)₂], [NiCl₂(PPh₃)₂], [NiBr₂(PPh₃)₂], [NiI₂(PPh₃)₂], [ZnCl₂(PPh₃)₂], [NiCl₂(PBz₃)₂], and [NiBr₂(PBz₃)₂]. A detailed geometric analysis revealed high isostructurality among several pairs. Ligand steric effects were assessed using cone angles and percentage surface coverage. Crystal packing is stabilized by weak C─H⋯π and C─H⋯X (X = Cl, Br, and I) interactions. Notably, [NiCl₂(PBz₃)₂] and [NiBr₂(PBz₃)₂] feature rare intramolecular C─H⋯Ni anagostic interactions. Reduced density gradient (RDG) and noncovalent interaction (NCI) plots confirmed weakly attractive C─H⋯π contacts in all complexes. Void-volume analysis assessed the mechanical strength of the crystals, while pixel energy and energy frameworks clarified structural stability and dominant interactions. Density Functional Theory (DFT) calculations, along with QTAIM/NCIplot and NBO analyses, as well as electron density (ED) versus electrostatic potential (ESP) plots, were performed to better understand the C─H···Ni interactions and distinguish between agostic and anagostic interactions.Fil: Pérez Pérez, Hiram. Universidad de La Habana; CubaFil: Gil, Diego Mauricio. Universidad Nacional de Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Orgánica; ArgentinaFil: Gomila, Rosa M.. Universidad de las Islas Baleares; EspañaFil: Frontera, Antonio. Universidad de las Islas Baleares; EspañaWiley2024-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/262786Pérez Pérez, Hiram; Gil, Diego Mauricio; Gomila, Rosa M.; Frontera, Antonio; Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations; Wiley; ChemistrySelect; 9; 45; 11-2024; 1-162365-6549CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/slct.202404665info:eu-repo/semantics/altIdentifier/doi/10.1002/slct.202404665info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:04:15Zoai:ri.conicet.gov.ar:11336/262786instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 12:04:15.519CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
title Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
spellingShingle Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
Pérez Pérez, Hiram
ANAGOSTIC INTERACTION
CRYSTAL VOIDS ENERGY
ISOSTRUCTURALITY
PHOSPINES
title_short Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
title_full Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
title_fullStr Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
title_full_unstemmed Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
title_sort Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations
dc.creator.none.fl_str_mv Pérez Pérez, Hiram
Gil, Diego Mauricio
Gomila, Rosa M.
Frontera, Antonio
author Pérez Pérez, Hiram
author_facet Pérez Pérez, Hiram
Gil, Diego Mauricio
Gomila, Rosa M.
Frontera, Antonio
author_role author
author2 Gil, Diego Mauricio
Gomila, Rosa M.
Frontera, Antonio
author2_role author
author
author
dc.subject.none.fl_str_mv ANAGOSTIC INTERACTION
CRYSTAL VOIDS ENERGY
ISOSTRUCTURALITY
PHOSPINES
topic ANAGOSTIC INTERACTION
CRYSTAL VOIDS ENERGY
ISOSTRUCTURALITY
PHOSPINES
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The crystal structures of seven metal dihalide complexes with triphenylphosphine (PPh₃) and two with tribenzylphosphine (PBz₃) have been reanalyzed. The studied complexes include [FeCl₂(PPh₃)₂], [CoCl₂(PPh₃)₂], [CoBr₂(PPh₃)₂], [NiCl₂(PPh₃)₂], [NiBr₂(PPh₃)₂], [NiI₂(PPh₃)₂], [ZnCl₂(PPh₃)₂], [NiCl₂(PBz₃)₂], and [NiBr₂(PBz₃)₂]. A detailed geometric analysis revealed high isostructurality among several pairs. Ligand steric effects were assessed using cone angles and percentage surface coverage. Crystal packing is stabilized by weak C─H⋯π and C─H⋯X (X = Cl, Br, and I) interactions. Notably, [NiCl₂(PBz₃)₂] and [NiBr₂(PBz₃)₂] feature rare intramolecular C─H⋯Ni anagostic interactions. Reduced density gradient (RDG) and noncovalent interaction (NCI) plots confirmed weakly attractive C─H⋯π contacts in all complexes. Void-volume analysis assessed the mechanical strength of the crystals, while pixel energy and energy frameworks clarified structural stability and dominant interactions. Density Functional Theory (DFT) calculations, along with QTAIM/NCIplot and NBO analyses, as well as electron density (ED) versus electrostatic potential (ESP) plots, were performed to better understand the C─H···Ni interactions and distinguish between agostic and anagostic interactions.
Fil: Pérez Pérez, Hiram. Universidad de La Habana; Cuba
Fil: Gil, Diego Mauricio. Universidad Nacional de Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Orgánica; Argentina
Fil: Gomila, Rosa M.. Universidad de las Islas Baleares; España
Fil: Frontera, Antonio. Universidad de las Islas Baleares; España
description The crystal structures of seven metal dihalide complexes with triphenylphosphine (PPh₃) and two with tribenzylphosphine (PBz₃) have been reanalyzed. The studied complexes include [FeCl₂(PPh₃)₂], [CoCl₂(PPh₃)₂], [CoBr₂(PPh₃)₂], [NiCl₂(PPh₃)₂], [NiBr₂(PPh₃)₂], [NiI₂(PPh₃)₂], [ZnCl₂(PPh₃)₂], [NiCl₂(PBz₃)₂], and [NiBr₂(PBz₃)₂]. A detailed geometric analysis revealed high isostructurality among several pairs. Ligand steric effects were assessed using cone angles and percentage surface coverage. Crystal packing is stabilized by weak C─H⋯π and C─H⋯X (X = Cl, Br, and I) interactions. Notably, [NiCl₂(PBz₃)₂] and [NiBr₂(PBz₃)₂] feature rare intramolecular C─H⋯Ni anagostic interactions. Reduced density gradient (RDG) and noncovalent interaction (NCI) plots confirmed weakly attractive C─H⋯π contacts in all complexes. Void-volume analysis assessed the mechanical strength of the crystals, while pixel energy and energy frameworks clarified structural stability and dominant interactions. Density Functional Theory (DFT) calculations, along with QTAIM/NCIplot and NBO analyses, as well as electron density (ED) versus electrostatic potential (ESP) plots, were performed to better understand the C─H···Ni interactions and distinguish between agostic and anagostic interactions.
publishDate 2024
dc.date.none.fl_str_mv 2024-11
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/262786
Pérez Pérez, Hiram; Gil, Diego Mauricio; Gomila, Rosa M.; Frontera, Antonio; Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations; Wiley; ChemistrySelect; 9; 45; 11-2024; 1-16
2365-6549
CONICET Digital
CONICET
url http://hdl.handle.net/11336/262786
identifier_str_mv Pérez Pérez, Hiram; Gil, Diego Mauricio; Gomila, Rosa M.; Frontera, Antonio; Revisiting Metal Dihalide Complexes with Phosphine Ligands: Isostructurality, Steric Effects, Anagostic Interactions, Crystal Voids, and Energetic Calculations; Wiley; ChemistrySelect; 9; 45; 11-2024; 1-16
2365-6549
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/slct.202404665
info:eu-repo/semantics/altIdentifier/doi/10.1002/slct.202404665
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.982451

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