Issue 5, 2023

Halogen bonding between metal-bound I3 and unbound I2: the trapped I2⋯I3 intermediate in the controlled assembly of copper(i)-based polyiodides

Abstract

Crystallization of [CuI(CNXyl)3] (1) with I2 (exhibiting strong halogen bond donor properties), at different molar ratios between the reactants, resulted in a series of (XylNC)CuI crystal polyiodides formed along with gradual accumulation of iodine, namely [Cu(I3)(CNXyl)3] (two crystalline polymorphs 2I and 2II), [Cu(I3)(CNXyl)3]·½I2 (2·½I2) and [Cu(CNXyl)3](I5) (3); all these compounds were studied by X-ray diffractometry. Molecular electrostatic potential (MEP) surface plots were also calculated using density functional theory (DFT) for isolated molecules of 2 and I2, showing electrophilic and nucleophilic sites. Halogen bonding in 2·½I2 was additionally elucidated for both crystal and cluster models, including combined quantum theory of atoms-in-molecules (QTAIM) and one-electron potential (OEP) projections. For model clusters, DFT energetic analysis, quantum theory of atoms-in-molecules, combined with the noncovalent interaction index plot (QTAIM/NCIplot), natural bond orbital (NBO) donor–acceptor charge transfer analysis, and Wiberg bond index (WBI) analysis were used. In the structure of 2·½I2, the presence of an I2⋯I3 halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I5 (and then I82−) ligands from I2 and metal-coordinated I3.

Graphical abstract: Halogen bonding between metal-bound I3− and unbound I2: the trapped I2⋯I3− intermediate in the controlled assembly of copper(i)-based polyiodides

Supplementary files

Article information

Article type
Research Article
Submitted
10 Dec. 2022
Accepted
11 Janv. 2023
First published
11 Janv. 2023

Inorg. Chem. Front., 2023,10, 1522-1533

Halogen bonding between metal-bound I3 and unbound I2: the trapped I2⋯I3 intermediate in the controlled assembly of copper(I)-based polyiodides

M. A. Kinzhalov, D. M. Ivanov, A. V. Shishkina, A. A. Melekhova, V. V. Suslonov, A. Frontera, V. Yu. Kukushkin and N. A. Bokach, Inorg. Chem. Front., 2023, 10, 1522 DOI: 10.1039/D2QI02634A

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