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The Pt (II)⋅⋅⋅Cl Interactions: Nature and Strength
Author(s) -
Lu Bo,
Zhang Xueying,
Meng Lingpeng,
Zeng Yanli
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601230
Subject(s) - chemistry , crystallography , halogen , hydrogen bond , platinum , metal , halogen bond , density functional theory , stereochemistry , computational chemistry , molecule , catalysis , organic chemistry , alkyl
The Pt (II)⋅⋅⋅Cl interactions between trans‐ Pt (NH 3 ) 2 X 2 / cis‐ Pt (NH 3 ) 2 X 2 (X=OH, F, Cl, Br) and ClF were constructed and studied by Møller‐Plesset perturbation theory (MP2) method. The metal Pt (II)‐complex could act as the halogen bond acceptor, the Pt (II)⋅⋅⋅Cl interaction strength depends on the nature and the configuration of platinum (II) ligands: the metal halogen‐bonding interactions in trans ‐Pt (OH) 2 (NH 3 ) 2 ⋅⋅⋅ClF/ cis ‐Pt (OH) 2 (NH 3 ) 2 ⋅⋅⋅ClF are obviously stronger than those in trans ‐PtX 2 (NH 3 ) 2 ⋅⋅⋅ClF/ cis ‐PtX 2 (NH 3 ) 2 ⋅⋅⋅ClF (X=F, Cl, Br); the halogen bonds in cis ‐complexes are somewhat stronger than those in respective trans ‐complexes. This particular Pt (II) ⋅⋅⋅ Cl interactions is much stronger than hydrogen bond and has some degree of covalent character. For the Pt (II)⋅⋅⋅Cl interactions, the charge transfer between the related molecular orbitals of PtX 2 (NH 3 ) 2 and ClF are obvious, which is consistent with that the exchange energy contributes most to the total interaction energy. The stronger of the Pt (II) ⋅⋅⋅ Cl interactions, the more decreased electron density outside Pt (II) facing the chlorine atom, and the more increased electron density between Pt (II) and Cl, indicating that the polarization effect plays an important role in the formation of the Pt (II) ⋅⋅⋅ Cl interactions.