Assembly of a dihydrideborate and two aryl nitriles to form a C, N, N''-Pincer Ligand Coordinated to Osmium

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

Resumen: The C, N, N''-donor aryl-diimineborate pincer ligand of the complexes OsH2{¿3-C, N, N-[C6H3RCH = NB(cat)N = CHC6H4R]}(PiPr3)2 (R = H, Me) has been generated in a one-pot procedure, by the reaction of the hexahydride OsH6(PiPr3)2 with catecholborane (catBH) and two molecules of the corresponding aryl nitrile. The osmium-pincer bonding situation has been analyzed by means of atoms in molecules (AIM), natural bond orbital (NBO), and energy decomposition analysis coupled with the natural orbitals for chemical valence (EDA-NOCV) methods. According to the results, the complexes exhibit a rather strong electron-sharing Os-C bond, two weaker donor-acceptor N-Os bonds, and two ?-back-donations from the transition metal to vacant p* orbitals of the formed metallacycles. In addition, spectroscopic findings and DFT calculations reveal that the donor units of the pincer are incorporated in a sequential manner. First, the central Os-N bond is formed, by the reaction of the dihydrideborate ligand of the intermediate OsH3{¿2-H, H-(H2Bcat)}(PiPr3)2 with one of the aryl nitriles. The subsequent oxidative addition of the o-C-H bond of the aryl substituent of the resulting ¿1-N-(N-boryl-arylaldimine) affords the Os-C bond. Finally, the second Os-N bond is generated from a hydride, an ortho-metalated N-boryl-arylaldimine, and the second aryl nitrile.

Idioma: Inglés

DOI: 10.1021/acs.organomet.0c00690

Año: 2021

Publicado en: Organometallics 40, 6 (2021), 635–642
ISSN: 0276-7333

Factor impacto JCR: 3.837 (2021)

Categ. JCR: CHEMISTRY, ORGANIC rank: 15 / 57 = 0.263 (2021) - Q2 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 12 / 46 = 0.261 (2021) - Q2 - T1

Factor impacto SCIMAGO: 0.994 - Organic Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E06-20R
Financiación: info:eu-repo/grantAgreement/ES/DGA/LMP148-18
Financiación: info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-78205-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/PID2019-106184GB-I00

Tipo y forma: Article (PostPrint)

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