| Abstract |
The complexes trans-[PtCl2 (NCNR2)(2)] (R-2 = Me-2 1, Et-2 2, (CH2)(4) 3) were cocrystallized with CBr4 in CHCl3 (1 and 3) or in MeNO2 (2) forming adducts 1 center dot CHCl3 center dot CBr4, 2.2CBr(4), and 3.2CBr(4), respectively. In two out of three adducts, viz. 1 center dot CHCl3 center dot CBr4 and 2.2CBr(4), unique Br3C-Br center dot center dot center dot eta(2)(Cl-Pt) metal-involving bifurcated halogen bonding was detected, by single-crystal XRD, along with other halomethane-chloride interactions. Appropriate density functional theory calculations performed by two complementary methodologies, (i) single-point quasi-solid state calculations with topological analysis of the electron density distribution within the framework of Bader theory (QTAIM method) and (ii) Kohn-Sham calculations with periodic boundary conditions, confirmed the existence of the bifurcated interactions and their noncovalent nature. Estimated energies of these interactions vary from 1.1 to 4.7 kcal/mol. |
