Halogen bond and polymorphism in <i>trans</i>-bis(2-iodo-5-halopyridine)dihalocopper(<scp>ii</scp>) complexes: crystallographic, theoretical and magnetic studies

Awwadi, Firas F.; Alwahsh, Manal I.; Turnbull, Mark M.; Landee, Christopher P.

doi:10.1039/d2ce01711c

Cited by 2 publications

(1 citation statement)

References 89 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An intramolecular chalcogen bond was found to control the geometry of substituted phenyl-SF 3 molecules. 52 A very recent study 53 showed how an internal XB controls the equilibrium between syn and anti conformers of trans-bis(2iodo-5-halopyridine)dihalocopper(II). Somewhat less explored to this point is the manner in which these same sorts of bonds affect the dynamics of the interconversion between structures of competing stabilities.…”

Section: ■ Introductionmentioning

confidence: 99%

Influence of Internal Noncovalent Bonds on Rotational Dynamics

Scheiner

2023

Inorg. Chem.

View full text Add to dashboard Cite

While a good deal of information has accumulated concerning the manner in which an intramolecular noncovalent bond can affect the relative energies of various conformers, less is known about how such bonds might affect the dynamics of interconversion between them. A series of molecules are constructed in which symmetrically equivalent conformers containing a noncovalent bond can be interconverted by a bond rotation, the energy barrier to which is computed by quantum chemical methods. The rotation of a CF3 group attached to a phenyl ring is speeded up if a Se··F chalcogen bond can be formed with a SeH or SeF group placed in an ortho position, a bond that is present in and stabilizes the rotational transition state. The analogous SnF3 group can, on the other hand, engage in a Sn··Se tetrel bond in its global minimum. The energetic cost of breakage of this bond is not fully compensated by the appearance of a Se··F chalcogen bond in the rotational transition state. Other systems were designed by placing two phenyl rings on opposite ends of an octahedrally disposed SeF4 group. A high barrier inhibits their rotation with bulky Br atoms in ortho positions, but this barrier is lowered if Br is replaced by groups that can engage in either chalcogen (SeH or SeF) or pnicogen (AsH2) bonds with the F atoms in the rotational transition state. The barrier reduction is closely related to the strength of these noncovalent bonds.

show abstract

Section: ■ Introductionmentioning

confidence: 99%