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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/262786
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CONICET Digital (CONICET) |
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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 Técnicas2025-09-29T10:31:49Zoai: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:34982025-09-29 10:31:49.302CONICET 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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1844614330057752576 |
score |
13.070432 |