Tetrabromoethane as σ-Hole Donor toward Bromide Ligands: Halogen Bonding between C2H2Br4 and Bromide Dialkylcyanamide Platinum(II) Complexes

Anna M Cheranyova,Daniil M Ivanov

doi:10.3390/cryst11070835

Abstract

The complexes trans-[PtBr2(NCNR2)2] (R2 = Me21, (CH2)52) were cocrystallized with 1,1,2,2-tetrabromoethane (tbe) in CH2Cl2 forming solvates 1·tbe and 2·tbe, respectively. In both solvates, tbe involved halogen bonding, viz. the C–Br···Br–Pt interactions, were detected by single-crystal X-ray diffractions experiments. Appropriate density functional theory calculations (M06/def2-TZVP) performed for isolated molecules and complex-tbe clusters, where the existence of the interactions and their noncovalent nature were confirmed by electrostatic potential surfaces (ρ = 0.001 a.u.) for isolated molecules, topology analysis of electron density, electron localization function and HOMO-LUMO overlap projections for clusters.

Highlights

In the past decade, the halogen bonding (XB) concept [1] has attracted a considerable attention as a new type of intermolecular interaction and has become an important tool for XB involving crystal engineering
We report our data on cocrystallization of tbe with dialkylcyanamide bromide complexes of platinum (II)
Electrostatic Surface atom,Potentials which we see for tbe

Summary

Introduction

The halogen bonding (XB) concept [1] has attracted a considerable attention as a new type of intermolecular interaction and has become an important tool for XB involving crystal engineering. The vast majority of XB studies do not utilize organometallic building blocks, these metal-containing species functioning as XB participants are very useful for the design of new supramolecular systems [7,8,9,10]. Involvement of various haloalkanes (in particular bromoalkanes) in the occurrence of XBs is among rapidly growing areas of XB based crystal engineering [3]. Perfluorinated bromoalkanes were found [11,12,13] to form XBs with metal-free halide anions. Dibromomethane [14,15], bromoform [16,17], tetrabromomethane [16,18,19] and hexabromoethane [20], functioning as XB acceptors, were studied toward halide ligands in metal complexes

Methods

Results

Conclusion