Evidence for a Bis(Elongated s)-Dihydrideborate Coordinated to Osmium

Babón, J.C. ; Esteruelas, M.A. ; Fernández, I. ; López, A.M. (Universidad de Zaragoza) ; Oñate, E.

Resumen: 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{¿2-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){¿2-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{¿2-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 s-borane-{bis(elongated s)-dihydrideborate}-osmium(II) derivative OsH(¿3-H2Bcat)(¿2-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·NH2 tBu) give OsH2(¿2:¿2-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.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.8b00155

Año: 2018

Publicado en: Inorganic Chemistry 57, 8 (2018), 4482-4491
ISSN: 0020-1669

Factor impacto JCR: 4.85 (2018)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 4 / 45 = 0.089 (2018) - Q1 - T1

Factor impacto SCIMAGO: 1.501 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E06-17R
Financiación: info:eu-repo/grantAgreement/ES/DGA/FSE
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-78205-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDC
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P

Tipo y forma: Artículo (PostPrint)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)