Regular/abnormal variation in the strength and nature of the halogen bond between H₂Te and the dihalogens: Prominent effect of methyl substituents

Abstract

The halogen‐bonded complexes between H2Te/Me2Te and the dihalogen molecules XY (XY = F2, Cl2, Br2, I2, ClF, ClBr, BrF, BrCl, BrI, IF, ICl, IBr) have been studied to investigate the dependence of its strength and nature on the halogen donor X and its adjoining atom Y, as well as the methyl groups in the electron donor. The interaction energy varies between −1.7 and − 43.5 kcal/mol, indicating that the Te atom in H2Te/Me2Te has a strong affinity for the dihalogen molecules. For the H2Te‐XY complex, the halogen bond is stronger for the heavier halogen donor X atom and the strong electron‐withdrawing group Y. However, for Me2Te‐XY, the halogen bond is stronger for the lighter halogen donor X atom. The H2Te/Me2Te‐F2 complex has the largest interaction energy, although the σ‐hole on F2 is the smallest in magnitude. In most of the complexes, the electrostatic and polarization contributions to the binding strength are similar in magnitude. However, for H2Te/Me2Te‐F2, the polarization contribution is much larger than the electrostatic contribution, with a significant contribution from charge transfer.

Molecular Main Group Metal Hydrides

“…The photodissociation of TeH 2 to form TeH • and a hydrogen radical has been examined in the gas phase, while the influence of spin-orbit coupling on the emission spectra of TeH has been studied . While not a molecular species, bulk TeH has been predicted to be superconducting at temperatures below 50 K at 300 GPa. , The interaction between TeH 2 and dihalogens, alkali metal cations, the tert -butyl cation ( t Bu + ), and the Criegee intermediate MeC­(H)­OO have been examined by DFT.…”

“…1395 While not a molecular species, bulk TeH has been predicted to be superconducting at temperatures below 50 K at 300 GPa. 1396,1397 The interaction between TeH 2 and dihalogens, 1398 alkali metal cations, the tert-butyl cation ( t Bu + ), 1399 and the Criegee intermediate MeC(H)OO 1400 have been examined by DFT. Organotellurols are less studied than their selenium congeners, however, the addition of n BuTeH to propargylic alcohols is known to give chiral enynes after postfunctionalization.…”