The H2C(X)–X•••X– (X = Cl, Br) Halogen Bonding of Dihalomethanes
Ivanov, D. M., Kinzhalov, M. A., Novikov, A. S., Ananyev, I. V., Romanova, A. A., Boyarskiy, V. P., . . . , & Kukushkin, V. Y. (2017). The H2C(X)–X•••X– (X = Cl, Br) Halogen Bonding of Dihalomethanes. Crystal Growth and Design, 17 (3), 1353-1362. doi:10.1021/acs.cgd.6b01754
Published in
Crystal Growth and DesignDate
2017Discipline
Epäorgaaninen ja analyyttinen kemiaCopyright
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by Elsevier. Published in this repository with the kind permission of the publisher.
The dihalomethane–halide H2C(X)–X···X– (X = Cl, Br) halogen bonding was detected in a series of the cis-[PdX(CNCy){C(NHCy)═NHC6H2Me2NH2}]X•CH2X2 (X = Cl, Br) associates by single-crystal XRD followed by DFT calculations. Although ESP calculations demonstrated that the σ-hole of dichloromethane is the smallest among all halomethane solvents (the maximum electrostatic potential is only 2.6 kcal/mol), the theoretical DFT calculations followed by Bader’s QTAIM analysis (M06/DZP-DKH level of theory) confirmed the H2C(X)–X···X– halogen bond in both the solid-state and gas-phase optimized geometries. The estimated bonding energy in H2C(X)–X···X– is in the 1.9–2.8 kcal/mol range.