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Hexaiododiplatinate(II) as a Useful Supramolecular Synthon for Halogen Bond Involving Crystal Engineering

Abstract

The hexaiododiplatinates(II) bearing ammonium and phosphonium cations, [R4N]2[Pt2(μ-I)2I4] {R = Et (1), n-Bu (2)} and [R3PR1]2[Pt2(μ-I)2I4] {R = n-Bu, R1 = n-Bu, (3); R = Ph, R1 = Ph (4); R = Ph, R1 = CH2Ph (5)}, were synthesized and characterized by high resolution ESI-MS, 1H, 13C{1H}, 31P{1H}, 195Pt NMR spectroscopies, Fourier transform infrared and Raman spectroscopies, X-ray diffraction (XRD), X-ray powder diffraction, and also by the electrostatic surface potential calculations. Complexes 13 were cocrystallized with halogen bond (XB) donors based on organic iodides featuring electron withdrawing groups {REWGIs: 1,3,5-triiodotrifluorobenzene (1,3,5-FIB), iodopentafluorobenzene (IPFB), 1,4-diiodotetrafluorobenzene (1,4-FIB), and tetraiodoethylene (C2I4)} to give crystalline adducts 1•2(1,3,5-FIB), 1•2IPFB, 2•2(1,4-FIB), and 3•C2I4. Inspection of the XRD data of the obtained adducts revealed the presence in all four structures of intermolecular REWGI•••I–Pt XBs between the iodine centers of REWGIs and the terminal iodide ligands of [Pt2(μ-I)2I4]2– anions, where the latter act as rectangular XB-accepting synthons forming XBs by two, three, and even four Pt–Iterminal ligands. Results of the Hirshfeld molecular surface analysis and density functional theory (DFT) calculations (M06/DZP-DKH level of theory) followed by topological analysis of the electron density distribution within the framework of Bader’s approach (QTAIM) confirmed the existence of the detected XBs, and their estimated energies vary from 2.2 to 4.7 kcal/mol.

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Publication details

The article was received on 31 Oct 2019, accepted on 02 Dec 2019 and first published on 03 Dec 2019


Article type: Paper
DOI: 10.1039/C9DT04221K
Dalton Trans., 2019, Accepted Manuscript

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    Hexaiododiplatinate(II) as a Useful Supramolecular Synthon for Halogen Bond Involving Crystal Engineering

    A. A. Eliseeva, D. M. Ivanov, A. S. Novikov, A. V. Rozhkov, I. V. Kornyakov, A. Yu. Dubovtsev and V. Yu. Kukushkin, Dalton Trans., 2019, Accepted Manuscript , DOI: 10.1039/C9DT04221K

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