Origin of the Ir-Si bond shortening in Ir-NSiN complexes

García-Orduña Pilar ; Fernández Israel ; Oro Luis A. (Universidad de Zaragoza) ; Fernández-Alvarez Francisco J. (Universidad de Zaragoza)

Resumen: The Ir–Si bond distances reported for Ir-(fac-κ3-NSiNOPy) and Ir-(fac-κ3-NSiN4MeOPy) species (NSiNOPy = bis(pyridine-2-yloxy)methylsilyl and NSiN4MeOPy = bis(4-methyl-pyridine-2-yloxy)methylsily) are in the range of 2.220–2.235 Å. These values are in the lowest limit of the Ir–Si bond distances found in the Cambridge Structural Database (CSD). To understand the origin of such remarkable shortening, a computational study of the bonding situation of representative examples of Ir-(fac-κ3-NSiN) species has been carried out. It is found that the Ir–Si bond can be described as an electron-sharing (i.e. covalent) bond. Despite that, this bond is highly polarized and as a result, the contribution of the electrostatic attractions to the bonding is rather significant. Indeed, there exists a linear relationship (R2 = 0.97) between the Ir–Si bond distance and the extent of the computed electrostatic interactions, which indicates that the ionic contribution to the bonding is mainly responsible for the observed Ir–Si bond shortening.

Idioma: Inglés

DOI: 10.1039/d1dt00473e

Año: 2021

Publicado en: Dalton Transactions 50, 17 (2021), 5951-5959
ISSN: 1477-9226

Factor impacto JCR: 4.569 (2021)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 7 / 46 = 0.152 (2021) - Q1 - T1

Factor impacto SCIMAGO: 0.864 - Inorganic Chemistry (Q1)

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

Tipo y forma: Artículo (PostPrint)

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