Synthesis and characterization of Ir-(k2-NSi) Species Active toward the solventless hydrolysis of HSiMe(OSiMe3)2

Gómez España, Alejandra ; García Orduña, Pilar ; Guzmán, Jefferson ; Fernández, Israel ; Fernández Álvarez, Francisco J. (Universidad de Zaragoza)

Resumen: The reaction of [IrH(Cl)(κ2-NSitBu2)(coe)] (1) with 1 equiv of PCy3 (or PHtBu2) gives the species [IrH(Cl)(κ2-NSitBu2)(L)] (L = PCy3, 2a; PHtBu2, 2b), which reacts with 1 equiv of AgOTf to afford [IrH(OTf)(κ2-NSitBu2)(L)] (L = PCy3, 3a and PHtBu2, 3b). Complexes 2a, 2b, 3a, and 3b have been characterized by means of NMR spectroscopy and HR-MS. The solid-state structures of complexes 2a, 2b, and 3a have been determined by X-ray diffraction studies. The reversible coordination of water to 3a, 3b, and 4 to afford the corresponding adduct [IrH(OTf)(κ2-NSitBu2)(L)(H2O)] (L = PCy3, 3a-H2O; PHtBu2, 3b-H2O; coe, 4-H2O) has been demonstrated spectroscopically by NMR studies. The structure of complexes 3b-H2O and 4-H2O have been determined by X-ray diffraction studies. Computational analyses of the interaction between neutral [NSitBu2]• and [Ir(H)L(X)]• fragments in Ir-NSitBu2 species confirm the electron-sharing nature of the Ir–Si bond and the significant role of electrostatics in the interaction between the transition metal fragment and the κ2-NSitBu2 ligand. The activity of Ir-(κ2-NSitBu2) species as catalysts for the hydrolysis of HSiMe(OSiMe3)2 depends on the nature of the ancillary ligands. Thus, while the triflate derivatives are active, the related chloride species show no activity. The best catalytic performance has been obtained when using complexes 3a, with triflate and PCy3 ligands, as a catalyst precursor, which allows the selective obtention of the corresponding silanol.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.2c01973

Año: 2022

Publicado en: Inorganic Chemistry 61, 41 (2022), 16282-16294
ISSN: 0020-1669

Factor impacto JCR: 4.6 (2022)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 5 / 42 = 0.119 (2022) - Q1 - T1

Factor impacto CITESCORE: 8.0 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.997 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PGC2018-099383-B-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T
Financiación: info:eu-repo/grantAgreement/ES/MINECO/PID2019-106184GB-I00

Tipo y forma: Artículo (Versión definitiva)

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