Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium

The formation and Atoms in Molecules (AIM) analysis of osmium(IV) and osmium(II) complexes containing dihydrideborate groups and primary aminoborane ligands are reported. Complex OsH6(PiPr3)2 (1) loses a hydrogen molecule and the resulting unsaturated OsH4(PiPr3)2 species coordinates 9-borabicycle[3...

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Autores: Babón, Juan C., Esteruelas, Miguel A., Fernández, Israel, López, Ana M., Oñate, Enrique
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/163662
Acesso em linha:http://hdl.handle.net/10261/163662
Access Level:acceso abierto
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spelling Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmiumBabón, Juan C.Esteruelas, Miguel A.Fernández, IsraelLópez, Ana M.Oñate, EnriqueThe formation and Atoms in Molecules (AIM) analysis of osmium(IV) and osmium(II) complexes containing dihydrideborate groups and primary aminoborane ligands are reported. Complex OsH6(PiPr3)2 (1) loses a hydrogen molecule and the resulting unsaturated OsH4(PiPr3)2 species coordinates 9-borabicycle[3.3.1]nonane (HBbn) and pinacolborane (HBpin) to give the dihydrideborate derivatives OsH3{κ2-H,H-(H2BR2)}(PiPr3)2 (BR2 = Bbn (2), Bpin (3)). The bonding situation in these compounds and in the related osmium(II) derivative Os(Bcat){κ2-H,H-(H2Bcat)}(CO)(PiPr3)2 (4) (HBcat = catecholborane) has been analyzed by the AIM method. The Laplacian distributions in the Os–H–B plane exhibit a four-membered cyclic topology possessing two Os–H and two B–H bond critical points associated with one OsHHB ring critical point, which resembles that found for B2H6. The tetrahydride OsH4(PiPr3)2 also coordinates catecholborane, which initially affords OsH3{κ2-H,H-(H2Bcat)}(PiPr3)2 (5). In contrast to 2 and 3, complex 5 reacts with a second molecule of HBcat to give the elongated σ-borane-{bis(elongated σ)-dihydrideborate}-osmium(II) derivative OsH(η3-H2Bcat)(η2-HBcat)(PiPr3)2 (6). Complexes 5 and 6 have been also analyzed via the AIM method. Complex 5 displays the same topology as complexes 2–4. However, the OsH2B unit of 6 shows, besides the Os–H and B–H bond critical points, an additional Os–B bond critical point, which is associated with a bond path running between these atoms. This double triangular topology is completed with the respective ring critical points. Reactions of 1 with dimethylamine–borane (H3B·NHMe2) and tert-butylamine–borane (H3B·NH2tBu) give OsH2(η2:η2-H2BNR2)(PiPr3)2 (NR2 = NMe2 (7), NHtBu (8)). The AIM analyses of 7 and 8 also reveal the occurrence of an Os–B bond critical point associated with a bond path running between those atoms. However, neither Os–H bond critical points nor bond paths are observed in the latter species.Financial support from the Spanish MINECO (Project Nos. CTQ2017-82935-P, CTQ2016-78205-P, Red de Excelencia Consolider CTQ2016-81797-REDC), Gobierno de Aragón (No. E06_17R), FEDER, and the European Social Fund (FSE) is acknowledged.Peer reviewedAmerican Chemical SocietyMinisterio de Economía y Competitividad (España)Agencia Estatal de Investigación (España)Gobierno de AragónEuropean CommissionConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201820182018info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/163662reponame: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##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-82935-PCTQ2017-82935-P/AEI/10.13039/501100011033info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-81797-REDCinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-78205-Phttps://doi.org/10.1021/acs.inorgchem.8b00155Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1636622026-05-22T06:33:51Z
dc.title.none.fl_str_mv Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
title Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
spellingShingle Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
Babón, Juan C.
title_short Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
title_full Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
title_fullStr Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
title_full_unstemmed Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
title_sort Evidence for a bis(elongated σ)-dihydrideborate coordinated to osmium
dc.creator.none.fl_str_mv Babón, Juan C.
Esteruelas, Miguel A.
Fernández, Israel
López, Ana M.
Oñate, Enrique
author Babón, Juan C.
author_facet Babón, Juan C.
Esteruelas, Miguel A.
Fernández, Israel
López, Ana M.
Oñate, Enrique
author_role author
author2 Esteruelas, Miguel A.
Fernández, Israel
López, Ana M.
Oñate, Enrique
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Agencia Estatal de Investigación (España)
Gobierno de Aragón
European Commission
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The formation and Atoms in Molecules (AIM) analysis of osmium(IV) and osmium(II) complexes containing dihydrideborate groups and primary aminoborane ligands are reported. Complex OsH6(PiPr3)2 (1) loses a hydrogen molecule and the resulting unsaturated OsH4(PiPr3)2 species coordinates 9-borabicycle[3.3.1]nonane (HBbn) and pinacolborane (HBpin) to give the dihydrideborate derivatives OsH3{κ2-H,H-(H2BR2)}(PiPr3)2 (BR2 = Bbn (2), Bpin (3)). The bonding situation in these compounds and in the related osmium(II) derivative Os(Bcat){κ2-H,H-(H2Bcat)}(CO)(PiPr3)2 (4) (HBcat = catecholborane) has been analyzed by the AIM method. The Laplacian distributions in the Os–H–B plane exhibit a four-membered cyclic topology possessing two Os–H and two B–H bond critical points associated with one OsHHB ring critical point, which resembles that found for B2H6. The tetrahydride OsH4(PiPr3)2 also coordinates catecholborane, which initially affords OsH3{κ2-H,H-(H2Bcat)}(PiPr3)2 (5). In contrast to 2 and 3, complex 5 reacts with a second molecule of HBcat to give the elongated σ-borane-{bis(elongated σ)-dihydrideborate}-osmium(II) derivative OsH(η3-H2Bcat)(η2-HBcat)(PiPr3)2 (6). Complexes 5 and 6 have been also analyzed via the AIM method. Complex 5 displays the same topology as complexes 2–4. However, the OsH2B unit of 6 shows, besides the Os–H and B–H bond critical points, an additional Os–B bond critical point, which is associated with a bond path running between these atoms. This double triangular topology is completed with the respective ring critical points. Reactions of 1 with dimethylamine–borane (H3B·NHMe2) and tert-butylamine–borane (H3B·NH2tBu) give OsH2(η2:η2-H2BNR2)(PiPr3)2 (NR2 = NMe2 (7), NHtBu (8)). The AIM analyses of 7 and 8 also reveal the occurrence of an Os–B bond critical point associated with a bond path running between those atoms. However, neither Os–H bond critical points nor bond paths are observed in the latter species.
publishDate 2018
dc.date.none.fl_str_mv 2018
2018
2018
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/10261/163662
url http://hdl.handle.net/10261/163662
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-82935-P
CTQ2017-82935-P/AEI/10.13039/501100011033
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-81797-REDC
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-78205-P
https://doi.org/10.1021/acs.inorgchem.8b00155
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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