Metal-Involving Bifurcated Halogen Bonding with Iodide and Platinum(II) Center
The cocrystallization of <i>trans</i>-[PtI<sub>2</sub>(NCR)<sub>2</sub>] (R = NMe<sub>2</sub><b>1</b>, NEt<sub>2</sub><b>2</b>, Ph <b>3</b>, o-ClC<sub>6</sub>H<sub>4</sub><b>4</b>) with iodine and iodoform gave the crystalline adducts <b>1</b>∙4I<sub>2</sub>, <b>2</b>∙2CHI<sub>3</sub>, <b>3</b>∙2CHI<sub>3</sub>, and <b>4</b>∙4I<sub>2</sub>, whose structures were studied by single-crystal X-ray diffractometry (XRD). In the structures, apart from the rather predictable C-H⋯I hydrogen bonds (HBs) and I-I⋯I or C-I⋯I halogen bonds (XBs) with the iodide ligands, we identified bifurcated I-I⋯(I-Pt) and C-I⋯(I-Pt) metal-involving XBs, where the platinum center and iodide ligands function as simultaneous XB acceptors toward σ-holes of I atoms in I<sub>2</sub> or CHI<sub>3</sub>. Appropriate density functional theory (DFT) calculations (PBE-D3/jorge-DZP-DKH with plane waves in the GAPW method) performed with periodic boundary conditions confirmed the existence of the bifurcated metal-involving I-I⋯(I-Pt) and C-I⋯(I-Pt) interactions and their noncovalent nature.
Authors
- Marina A. Khazanova
- Mariya A. Kryukova (ORCID: https://orcid.org/0000-0002-5515-7780)
- Anna M. Cheranyova (ORCID: https://orcid.org/0000-0002-4330-4624)
- Anton V. Rozhkov (ORCID: https://orcid.org/0000-0002-8658-7281)
- Daniil M. Ivanov (ORCID: https://orcid.org/0000-0002-0855-2251)
- Margarita B. Kostareva (ORCID: https://orcid.org/0009-0000-8294-7836)
Institutions
- St Petersburg University (RU)
Publication Details
- Journal
- International Journal of Molecular Sciences
- Published
- 2025-05-09
- DOI
- https://doi.org/10.3390/ijms26104555
- Citations
- 5
- Primary Topic
- Crystallography and molecular interactions
- Type
- article
- Field-Weighted Citation Impact
- 8.76
Funders
- Russian Science Foundation
- Division of Materials Research