Structure and bonding of halonium compounds

Velasquez, J. D. ; Echeverría, J. (Universidad de Zaragoza) ; Álvarez, S.

Resumen: The geometrical parameters and the bonding in [D···X···D]+ halonium compounds, where D is a Lewis base with N as the donor atom and X is Cl, Br, or I, have been investigated through a combined structural and computational study. Cambridge Structural Database (CSD) searches have revealed linear and symmetrical [D···X···D]+ frameworks with neutral donors. By means of density functional theory (DFT), molecular electrostatic potential (MEP), and energy decomposition analyses (EDA) calculations, we have studied the effect of various halogen atoms (X) on the [D···X···D]+ framework, the effect of different nitrogen-donor groups (D) attached to an iodonium cation (X = I), and the influence of the electron density alteration on the [D···I···D]+ halonium bond by variation of the R substituents at the N-donor upon the symmetry, strength, and nature of the interaction. The physical origin of the interaction arises from a subtle interplay between electrostatic and orbital contributions (σ-hole bond). Interaction energies as high as 45 kcal/mol suggest that halonium bonds can be exploited for the development of novel halonium transfer agents, in asymmetric halofunctionalization or as building blocks in supramolecular chemistry.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.3c00654

Año: 2023

Publicado en: Inorganic Chemistry 62, 23 (2023), 8980-8992
ISSN: 0020-1669

Factor impacto JCR: 4.3 (2023)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 8 / 44 = 0.182 (2023) - Q1 - T1

Factor impacto CITESCORE: 7.6 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1)

Factor impacto SCIMAGO: 0.928 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FSE/E07-20R
Financiación: info:eu-repo/grantAgreement/ES/MCINN/PID2019-109119GA-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CEX2021-001202-M
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RYC-2017-22853

Tipo y forma: Article (Published version)

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