Work

Halogen Bond‐Driven Ligand Displacement: Co‐Crystal Lattice Versus Coordination Bonds

Year: 2025

Type: article

Abstract: Coordination bonds are generally stronger than halogen bonds; however, the Jahn–Teller effect in d⁹ Cu(II) and the trans influence of the oxo‐ligand in vanadyl (V═O) acetylacetonates can weaken N→Cu/V bonds, bringing them closer to the upper range of halogen bond strength. The study investigates the interactions between transition metal acetylacetonate complexes, M(acac) 2 (L) (M─Cu(II), V(IV) = O; L = amine ligands), and halogen bond (XB)‐donor co‐formers, particularly 1,4‐diiodotetrafluorobenzene (1,4‐DITFB). The co‐crystallization experiments reveal an unusual ligand displacement phenomenon wherein the expected M(acac) 2 (L)·1,4‐DITFB complexes fail to form, instead yielding separate M(acac) 2 ·1,4‐DITFB and L·1,4‐DITFB co‐crystals. Computational studies reveal that while XB interactions alone may be insufficient to disrupt the M─N coordination bond, they can induce ligand displacement when amplified by the lattice stabilization of the resulting halogen‐bonded co‐crystals, particularly in Jahn–Teller distorted d⁹ Cu(II) and trans‐influenced V(IV) = O complexes interacting with halogen bond donors.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.202404784

Authors: Yury V. Torubaev, Omer Shaashua, Savion Braunstein, Doron Pappo

Institution: Ben-Gurion University of the Negev

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,640

Funder: Israel Science Foundation