Cleavage of the Pt-I bond in a Primary Cycloplatinated Amine by Chelation

Raven, William; Kalf, Irmgard; Englert, Ulli

doi:10.3390/cryst5020244

Cited by 3 publications

(1 citation statement)

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“…In 2008, we reported the first convenient route to cycloplatination of primary amines via a mixed‐valent platinum iodide precursor [14] . This reaction paved the way to a new class of compounds: The σ donor and iodo ligands in the primary cycloplatination product 1 (Scheme 1) may be substituted, [14,15] a chelating ligand may replace these two monodentate substituents, [16] and Pt(IV) complexes are accessible via oxidative addition [17] . Dehalogenation of 1 with the Ag(I) salt of a weakly coordinated anion affords the aqua complex 2 [15] .…”

Section: Introductionmentioning

confidence: 99%

Bimetallic Organoplatinum(II)‐Ag(I) Cluster Cations with Ag−Pt Interactions Unsupported by Conventional Bridging Ligands

Raven

Kalf

Paulmann

et al. 2022

Zeitschrift anorg allge chemie

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The organoplatinum complex of a primary amine and AgClO 4 aggregate in methanol to oligonuclear mixed-metal species. A perchlorate salt 3 with the empirical formula C 96 H 146 Ag 7 Cl 13 N 12 O 62 Pt 6 could be isolated and structurally characterized with the help of X-ray diffraction at the DESY synchrotron. The product contains both a penta-and a tetranuclear complex cation in which Ag(I) and Pt(II) alternate, held together without any conventional bridge. The cationic species feature short Ag•••Pt distances between 2.7 and 2.9 Å and contacts longer than 2.4 Å between Ag and C atoms in aromatic rings. In addition to the interactions with Ag(I) cations, Pt(II) is in a square-planar arrangement, coordinated by a chelating and a terminal amine and an aqua ligand. The central Ag(I) in the pentanuclear cation is located on a twofold crystallographic axis and not involved in any obvious coordinative bond; it exclusively shows short contacts to the neighboring Pt(II) ions and the Pt-bonded, formally anionic carbon atoms of the cyclometallated organic ligand. Powder diffraction shows that 3 melts and re-solidifies without decomposition.

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Section: Introductionmentioning

confidence: 99%

Bimetallic Organoplatinum(II)‐Ag(I) Cluster Cations with Ag−Pt Interactions Unsupported by Conventional Bridging Ligands

Raven

Kalf

Paulmann

et al. 2022

Zeitschrift anorg allge chemie

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Anisotropic displacement parameters from dispersion-corrected DFT methods and their experimental validation by temperature-dependent X-ray diffraction

George

Deringer

et al. 2015

CrystEngComm

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In chemical crystallography, the thermal motion of scattering centres is commonly described by anisotropic displacement parameters (ADPs). Very recently, it has been shown that ADPs are not only accessible by diffraction experiments but also via theory: this emerging approach seems promising but must be thoroughly tested. In this study, we have performed specifically tailored X-ray diffraction (XRD) experiments in fine steps between 100 and 300 K which allow detailed comparison to ab initio data from dispersion-corrected density functional theory (DFT) combined with periodic lattice-dynamics. The compound chosen for this study, crystalline pentachloropyridine ĲC 5 NCl 5 ), is well suited for this purpose: it represents a molecular crystal without H atoms, thus posing no challenge to XRD; its solid-state structure is controlled by dispersion and halogen-bonding interactions; and the ADPs associated with the peripheral Cl atoms show strong temperature dependence. Quality criteria in direct and in reciprocal space prove that ADPs are predicted with high confidence for the temperature range between 100 and 200 K, and that several economic dispersion corrections to DFT can be reliably employed for this purpose. Within the limits we have explored here, the ab initio prediction of ADPs appears to be a facile and complementary tool, especially in those cases where diffraction data cannot provide a straightforward model for thermal motion.7414 | CrystEngComm, 2015, 17, 7414-7422This journal is

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Hydrogenversusfluorine: effects on molecular structure and intermolecular interactions in a platinum isocyanate complex

et al. 2016

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At the molecular level, the enantiomerically pure square-planar organoplatinum complex (SP-4-4)-(R)-[2-(1-aminoethyl)-5-fluorophenyl-κ(2)C(1),N][(R)-1-(4-fluorophenyl)ethylamine-κN](isocyanato-κN)platinum(II), [Pt(C8H9FN)(NCO)(C8H10FN)], and its congener without fluorine substituents on the aryl rings adopt the same structure within error. The similarities between the compounds extend to the most relevant intermolecular interactions, i.e. N-H...O and N-H...N hydrogen bonds link neighbouring molecules into chains along the shortest lattice parameter in each structure. Differences between the crystal structures of the fluoro-substituted and parent complex become obvious with respect to secondary interactions perpendicular to the classical hydrogen bonds; the fluorinated compound features short C-H...F contacts with an F...H distance of ca 2.6 Å. The fluorine substitution is also reflected in reduced backbonding from the metal cation to the isocyanate ligand.

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Cleavage of the Pt-I bond in a Primary Cycloplatinated Amine by Chelation

Cited by 3 publications

References 14 publications

Bimetallic Organoplatinum(II)‐Ag(I) Cluster Cations with Ag−Pt Interactions Unsupported by Conventional Bridging Ligands

Bimetallic Organoplatinum(II)‐Ag(I) Cluster Cations with Ag−Pt Interactions Unsupported by Conventional Bridging Ligands

Anisotropic displacement parameters from dispersion-corrected DFT methods and their experimental validation by temperature-dependent X-ray diffraction

Hydrogenversusfluorine: effects on molecular structure and intermolecular interactions in a platinum isocyanate complex

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