Towards a Stronger Halogen Bond Involving Astatine: Unexpected Adduct with Bu 3 PO Stabilized by Hydrogen Bonding

Halogen Bonding versus Hydrogen Bonding: A Molecular Orbital Perspective

We have carried out extensive computational analyses of the structure and bonding mechanism in trihalides DX⋅⋅⋅A(-) and the analogous hydrogen-bonded complexes DH⋅⋅⋅A(-) (D, X, A=F, Cl, Br, I) using relativistic density functional theory (DFT) at zeroth-order regular approximation ZORA-BP86/TZ2P. One purpose was to obtain a set of consistent data from which reliable trends in structure and stab...

Carbon–Halogen Bond Activation by Selenium‐Based Chalcogen Bonding

Chalcogen bonding is a little explored noncovalent interaction similar to halogen bonding. This manuscript describes the first application of selenium-based chalcogen bond donors as Lewis acids in organic synthesis. To this end, the solvolysis of benzhydryl bromide served as a halide abstraction benchmark reaction. Chalcogen bond donors based on a bis(benzimidazolium) core provided rate acceler...

Hydrogen bonding vs. halogen bonding: the solvent decides.

Control of intermolecular interactions is integral to harnessing self-assembly in nature. Here we demonstrate that control of the competition between hydrogen bonds and halogen bonds, the two most highly studied directional intermolecular interactions, can be exerted by choice of solvent (polarity) to direct the self-assembly of co-crystals. Competitive co-crystal formation has been investigate...

Halogen Bonding versus Hydrogen Bonding: A Molecular Orbital Perspective Previously appeared as Halogen Bonding versus Hydrogen Bonding: A Molecular Orbital Perspective

Redox-induced fluoride ligand dissociation stabilized by intramolecular hydrogen bonding.

Chemical reduction of a tripodal Cu(II)-F complex containing pendent hydroxyl groups results in the partial dissociation of a F(-) ligand from Cu. The resulting Cu(I) complex is characterized as containing an outer sphere F(-) anion 'captured' by hydrogen bonds. The pendent hydroxyl groups were found to be crucial for reductive stability.