Browsing by Subject "LIGANDS"

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  • Schlindwein, Simon H.; Sibold, Carlo; Schenk, Mareike; Ringenberg, Mark R.; Feil, Christoph M.; Nieger, Martin; Gudat, Dietrich (2020)
    The ability of 3-(diphenylphosphinomethyl)-benzene-1,2-dithiol (pbdtH(2)) to act as ditopic ligand was probed in reactions with selected group-10-metal complexes. Reactions with [(cod)PdCl2] afforded a mixture of products identified as [Pd(pbdtH)(2)], [Pd-2(mu(2)-pbdt)(2)] and [Pd-3(mu(2)-pbdt)(2)Cl-2]. The polynuclear complexes could be isolated after suitably adjusting the reaction conditions, and heating of a mixture in a microwave reactor effected partial conversion into a further complex [Pd-3(mu(2)-pbdt)(3)]. Reaction of pbdtH(2) with [Ni(H2O)(6)Cl-2] gave rise to a complex [Ni-2(mu(2)-pbdt)(2)], which was shown to undergo two reversible 1e(-)-reduction steps. Reaction of [Pd(pbdtH)(2)] with [Au(PPh3)Cl] afforded heterotrinuclear [PdAu2(mu(2)-pbdt)(2)(PPh3)]. All complexes were characterized by analytical, spectroscopic and single-crystal X-ray diffraction studies. Their molecular structures confirm the ability of the pbdt(2-) unit to support simultaneous P,S- and S,S-chelating coordination to two metal centers.
  • Weller, Stefan; Schlindwein, Simon H.; Feil, Christoph M.; Kelemen, Zsolt; Buzsaki, Daniel; Nyulaszi, Laszlo; Isenberg, Stefan; Pietschnig, Rudolf; Nieger, Martin; Gudat, Dietrich (2019)
    Reactions of P-chloro-1,3,2-diazaphospha[3]ferrocenophanes with ECl3 (E = Al, Ga) under solvent-free conditions and with Na[Mn(CO)(5)] furnished salts featuring a ferrocenophane-based phosphenium cation and neutral phosphenium complexes, respectively. All products were characterized by spectroscopic studies. Single-crystal X-ray diffraction studies confirmed the ionic nature of the phosphenium tetrachloroaluminate and the structural analogy between the phosphenium complexes and Fischer-type carbene complexes. Distinct deviations in the conformation of the ansa bridge suggest electronic stabilization of the electrophilic phosphorus atom by phosphorus-nitrogen pi interactions in the free cation and by phosphorus-metal pi bonding in the complexes. The observation of short intermolecular contacts in the crystalline phosphenium salt and its chemical behavior toward donor solvents attest to the cation having an unusually high degree of Lewis acidity, which was confirmed by DFT studies and related to the presence of a rather large N-P-N angle. Computational studies indicate further that the free phosphenium cation exhibits a closed-shell electronic structure with a formal Fe(II) oxidation state and is thus a true analogue to ferrocenophane-based diaminotetrylenes.
  • Knoll, Daniel M.; Zippel, Christoph; Hassan, Zahid; Nieger, Martin; Weis, Patrick; Kappes, Manfred M.; Braese, Stefan (2019)
    We report the synthesis and catalytic application of a highly stable distance-defined Au/Ru heterobimetallic complex. [2.2]Paracyclophane serves as a backbone, holding the two metal centers in a spatial orientation and metal-metal fixed distance. The Au/Ru heterobimetallic complex is highly stable, easily accessible and exhibits promising catalytic activity in a visible-light mediated dual Au/Ru Meyer-Schuster rearrangement.
  • Stadelmann, B.; Bender, J.; Förster, D.; Frey, W.; Nieger, M.; Gudat, D. (2015)
    A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)(4)]/NaH and characterized by spectral and XRD data. The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalent of an N-heterocyclic chlorophosphine proceed via electrophilic functionalization at the metal site to yield appropriate mono- or bis-phosphenium complexes. Reaction with MeI at -70 degrees C produces a P-alkylation product as the first spectroscopically detectable intermediate, which decays at a higher temperature to give a mixture of free P-methylated N-heterocyclic phosphine and its Fe(CO)(4) complex. The different reaction products were characterized by spectral and XRD data. Computational studies indicate that the NHP units in all complexes display p-acceptor behaviour but show no disposition to adopt phosphide-like character or formally oxidize the metal centre.
  • Freese, Tyll; Lücke, Ana-Luiza; Schmidt, Catharina A. S.; Polamo, Mika; Nieger, Martin; Namyslo, Jan C.; Schmidt, Andreas (2017)
    The sydnone imines Molsidomine and 5-(benzoylimino)-3-(2-methoxyphenyl)-1,2,3-oxadiazolium-2-ide gave anionic N-heterocyclic carbenes on deprotonation at C4 which were trapped as methylated selenium adducts, gold complexes (X-ray analysis) as well as palladium complexes (X-ray analysis). The C-13 NMR resonance frequencies of the carbene carbon atom are extremely shifted upfield and appear at delta = 142.1 ppm (Molsidomine carbene) and delta = 159.8 ppm (sydnone imine carbene). The Pd complexes were applied as catalysts in Suzuki-Miyaura and Sonogashira-Hagihara cross-coupling reactions. (C) 2017 Elsevier Ltd. All rights reserved.
  • Leino, Teppo O.; Turku, Ainoleena; Yli-Kauhaluoma, Jari Tapani; Kukkonen, Jyrki P.; Xhaard, Henri; Wallén, Erik A. A. (2018)
    A library of 70 000 synthetically accessible azulene-based compounds was virtually screened at the OX2 receptor. Based on the results, a series of azulene derivatives was synthesized and the binding to and activation of both orexin receptor subtypes were assessed. Two most promising binders were determined to have inhibition constants in the 3-9 mu M range and two other compounds showed weak OX2 receptor agonism. Furthermore, three compounds exhibited a concentration-dependent potentiation of the response to orexin-A at the OX1 but not the OX2 receptors. Altogether this data opens new approaches for further development of antagonists, agonists, and potentiators of orexin response based on the azulene scaffold. (C) 2018 Elsevier Masson SAS. All rights reserved.
  • Blum, Markus; Gebhardt, Jacqueline; Papendick, Marius; Schlindwein, Simon H.; Nieger, Martin; Gudat, Dietrich (2018)
    Two N-heterocyclic phosphines with exocyclic SCN substituents were synthesised via metathesis of chlorophosphine precursors with KSCN and fully characterised. The crystallographic studies reveal that the products exhibit pronounced structural differences. The thiocyanato unit binds in one case via the nitrogen atom to yield a molecular structure with a slightly elongated P-N single bond and, in the other case, via the sulfur atom to form a structure that is best described as an ion pair and forms a one-dimensional coordination polymer in the crystal. DFT calculations suggest that the P-N and P center dot center dot center dot S interactions can be described as covalent and dative bonds, respectively, and that the structural differences correlate with the different cation stabilities of the individual phosphenium cation fragments.
  • Wallesch, Manuela; Nieger, Martin; Volz, Daniel; Bräse, Stefan (2017)
    Copper(I) complexes are studied for various potential applications due to their luminescence properties. However, issues have been identified regarding the stability of heteroleptic compounds. As a novel strategy, we propose to modify existing copper(I) complexes by introduction of molecular bridges between the different ligands. We report the synthesis and chemical properties of the complexes of 8-(diphenylphosphanyl-oxy)quinoline (POQ), a combination of a phosphine and a N-heterocycle with CuX (X = Cl, Br, I and SCN). The photophysical properties of the materials were studied. However, all four compounds were found to be labile in solution upon contact with trace amounts of water. Two POQ complexes and the decomposition products were identified as tetraphenyldiphosphoxane complexes with single crystal X-ray diffraction. We propose a design rule to prevent this behavior in future development steps. (C) 2017 Published by Elsevier B.V.
  • Shakirova, Julia R.; Sadeghi, Amir; Koblova, Alla A.; Chelushkin, Pavel S.; Toropainen, Elisa; Tavakoli, Shirin; Kontturi, Leena-Stiina; Lajunen, Tatu; Tunik, Sergey P.; Urtti, Arto (2020)
    Two iridium [Ir(NC)(2)(NN)](+) complexes with the diimine NN ligand containing a long polymethylene hydrophobic chain were synthesized and characterized by using NMR and ESI mass-spectrometry: NN - 2-(1-hexadecyl-1H-imidazol-2-yl)pyridine, NC - methyl-2-phenylquinoline-4-carboxylate (Ir1) and 2-phenylquinoline-4-carboxylic acid (Ir2). These complexes were used to prepare the luminescent PEGylated DPPC liposomes (DPPC/DSPE-PEG2000/Ir-complex = 95/4.5/1 mol%) using a thin film hydration method. The narrowly dispersed liposomes had diameters of about 110 nm. The photophysics of the complexes and labeled liposomes were carefully studied. Ir1 and Ir2 give red emission (lambda(em) = 667 and 605 nm) with a lifetime in the microsecond domain and quantum yields of 4.8% and 10.0% in degassed solution. Incorporation of the complexes into the liposome lipid bilayer results in shielding of the emitters from interaction with molecular oxygen and partial suppression of excited state nonradiative relaxation due to the effect of the relatively rigid bilayer matrix. Delivery of labeled liposomes to the cultured ARPE-19 cells demonstrated the usefulness of Ir1 and Ir2 in cellular imaging. Labeled liposomes were then injected intravitreally into rat eyes and imaged successfully with optical coherence tomography and funduscopy. In conclusion, iridium complexes enabled the successful labeling and imaging of liposomes in cells and animals.
  • Liu, Ming; Namyslo, Jan C.; Nieger, Martin; Polamo, Mika; Schmidt, Andreas (2016)
    The mesomeric betaine imidazolium-1-ylphenolate forms a borane adduct with tris(pentafluorophenyl) borane by coordination with the phenolate oxygen, whereas its NHC tautomer 1-(2-phenol) imidazol-2-ylidene reacts with (triphenylphosphine) gold(I) chloride to give the cationic NHC complex [Au(NHC)(2)][Cl] by coordination with the carbene carbon atom. The anionic N-heterocyclic carbene 1-(2-phenolate) imidazol-2-ylidene gives the complexes [K][Au(NHC-)(2)], [Rh(NHC-)(3)] and [Ni(NHC-)(2)], respectively. Results of four single crystal analyses are presented.
  • Boden, Pit; Di Martino-Fumo, Patrick; Busch, Jasmin M.; Rehak, Florian R.; Steiger, Sophie; Fuhr, Oliver; Nieger, Martin; Volz, Daniel; Klopper, Willem; Bräse, Stefan; Gerhards, Markus (2021)
    To develop new and flexible Cu-I containing luminescent substances, we extend our previous investigations on two metal-centered species to four metal-centered complexes. These complexes could be a basis for designing new organic light-emitting diode (OLED) relevant species. Both the synthesis and in-depth spectroscopic analysis, combined with high-level theoretical calculations are presented on a series of tetranuclear Cu-I complexes with a halide containing Cu4X4 core (X=iodide, bromide or chloride) and two 2-(diphenylphosphino)pyridine bridging ligands with a methyl group in para (4-Me) or ortho (6-Me) position of the pyridine ring. The structure of the electronic ground state is characterized by X-ray diffraction, NMR, and IR spectroscopy with the support of theoretical calculations. In contrast to the para system, the complexes with ortho-substituted bridging ligands show a remarkable and reversible temperature-dependent dual phosphorescence. Here, we combine for the first time the luminescence thermochromism with time-resolved FTIR spectroscopy. Thus, we receive experimental data on the structures of the two triplet states involved in the luminescence thermochromism. The transient IR spectra of the underlying triplet metal/halide-to-ligand charge transfer (M-3/XLCT) and cluster-centered ((CC)-C-3) states were obtained and interpreted by comparison with calculated vibrational spectra. The systematic and significant dependence of the bridging halides was analyzed.
  • Blum, M.; Puntigam, O.; Plebst, S.; Ehret, F.; Bender, J.; Nieger, M.; Gudat, D. (2016)
    The homolytic P-P bond fission in a series of sterically congested tetraaminodiphosphanes (R2N)(2)P-P-(NR2)(2) ({4}(2)-{9}(2), two of which were newly synthesized and fully characterized) into diaminophosphanyl radicals (R2N)(2)P-center dot (4-9) was monitored by VT EPR spectroscopy. Determination of the radical concentration from the EPR spectra permitted to calculate free dissociation energies Delta G(Diss)(295) as well as dissociation enthalpies Delta H-Diss and entropies Delta S-Diss, respectively. Large positive values of Delta G(Diss)(295) indicate that the degree of dissociation is in most cases low, and the concentration of persistent radicals - even if they are spectroscopically observable at ambient temperature - remains small. Appreciable dissociation was established only for the sterically highly congested acyclic derivative {9}(2). Analysis of the trends in experimental data in connection with DFT studies indicate that radical formation is favoured by large entropy contributions and the energetic effect of structural relaxation (geometrical distortions and conformational changes in acyclic derivatives) in the radicals, and disfavoured by attractive dispersion forces. Comparison of the energetics of formation for CC-saturated N-heterocyclic diphosphanes and the 7 pi-radical 3c indicates that the effect of energetic stabilization by pi-electron delocalization in the latter is visible, but stands back behind those of steric and entropic contributions. Evaluation of spectroscopic and computational data indicates that diaminophosphanyl radicals exhibit, in contrast to aminophosphenium cations, no strong energetic preference for a planar arrangement of the (R2N)(2)P unit.
  • Zippel, Christoph; Bartholomeyzik, Teresa; Friedmann, Christian; Nieger, Martin; Hassan, Zahid; Brase, Stefan (2021)
    In this report, we describe a series of cyclophanyl-derived mono- and binuclear N,C-palladacycles by regioselective ortho-palladation of amine-functionalized [2.2]paracyclophanes. Employing Pd(OAc)(2) followed by LiCl and with the subsequent modular treatment of Ph3P, Cy3P, and (Ph2PCH2)(2), this strategy allows to prepare stable cyclophanyl-derived planar and central chiral N,C-palladacycles in a highly selective manner. The regioselective ortho-palladation mono- and bimetallic product formation was analyzed by detailed spectroscopic techniques, mass spectrometry and unambiguously confirmed by single-crystal X-ray analysis.
  • Birchall, Nicholas; Feil, Christoph M.; Gediga, Michael; Nieger, Martin; Gudat, Dietrich (2020)
    The reversible reaction of H(2)with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2)and yields a spectroscopically detectable phosphenium-stabilized (sigma-H-2)-complex, readily showing exchange with gaseous H(2)and D-2. Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H(2)cleavage across a 3d MP bond. The same species is also accessibleviastepwise H+/H(-)transfer to the bis-phosphenium complex, and releases H(2)upon heating or irradiation. Dihydrogen transfer from the H-2-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex.
  • Schlindwein, Simon H.; Nieger, Martin; Gudat, Dietrich (2021)
    Reaction of a phosphane-decorated benzenedithiol (pbdtH(2)) with coinage metal salts furnished polynuclear complexes [M-2(pbdtH)(2)] (M=Au-I) or [cat][M-5(pbdt)(3)] (cat=unipositive cation, M=Ag-I, Cu-I), which were characterized by analytical and spectroscopic techniques and single-crystal X-ray diffraction studies. Furthermore, a double salt with an anion [Ag-5(pbdt)(3)(PPh3)](-) that proved unstable in solution was characterized crystallographically. The spectroscopic and crystallographic data revealed that the Cu(I) and Ag(I) complexes exhibit, despite their like stoichiometric composition, isomeric molecular structures. The observed disparities were reproduced by DFT studies. The dinuclear Au(I) complex was found to undergo air-oxidation to furnish a mixed-valent complex [(Au-III)(2)(Au-I)(2)(pbdt)(4)]. The copper(I) - but not the isomeric silver(I) complexes - showed luminescence in the solid state.
  • Karhu, Lasse; Weisell, Janne; Turunen, Pauli M.; Leino, Teppo O.; Pätsi, Henri; Xhaard, Henri; Kukkonen, Jyrki P.; Wallén, Erik A.A. (2018)
    The peptides orexin-A and -B, the endogenous agonists of the orexin receptors, have similar 19-amino-acid C-termini which retain full maximum response as truncated peptides with only marginally reduced potency, while further N-terminal truncations successively reduce the activity. The peptides have been suggested to bind in an α‐helical conformation, and truncation beyond a certain critical length is likely to disrupt the overall helical structure. In this study, we set out to stabilize the α‐helical conformation of orexin‐A15–33 via peptide stapling at four different sites. At a suggested hinge region, we varied the length of the cross-linker as well as replaced the staple with two α-aminoisobutyric acid residues. Modifications close to the peptide C‐terminus, which is crucial for activity, were not allowed. However, central and N‐terminal modifications yielded bioactive peptides, albeit with decreased potencies. This provides evidence that the orexin receptors can accommodate and be activated by α-helical peptides. The decrease in potency is likely linked to a stabilization of suboptimal peptide conformation or blocking of peptide backbone–receptor interactions at the hinge region by the helical stabilization or the modified amino acids.
  • Papendick, Marius; Feil, Christoph M.; Nieger, Martin; Gudat, Dietrich (2018)
    Metathesis of Na[Mn(CO)(5)] with N-tBu and N-Mes substituted, electrophilic N-heterocyclic phosphane derivatives afforded in the first case an ionic N-heterocyclic phosphenium (NHP) metalate and in the second case a covalent phosphenium complex. The products were characterized by analytical and spectroscopic data and the NHP complex as well by a single-crystal X-ray diffraction study. A DFT study allows relating the different outcome of the reactions studied with the energetics of the decarbonylation of the appropriate NHP metalates. Closer evaluation reveals steric factors as the key to explaining the observed behavior, and indicates that their impact displays close parallels to NHC chemistry.
  • Wiechmann, Sascha; Freese, Tyll; Drafz, Martin H. H.; Hübner, Eike G.; Namyslo, Jan C.; Nieger, Martin; Schmidt, Andreas (2014)
  • Joost, Maximilian; Nieger, Martin; Lutz, Martin; Ehlers, Andreas W.; Slootweg, Jacob Christiaan (Chris); Lammertsma, Koop (2020)
    O- and S-heterocyclic carbenes (OHCs, SHCs) are shown experimentally and computationally to be stronger pi acceptors than NHCs and lack, of course, substituents at the heteroatoms. These different electronic and steric characteristics make OHCs and SHCs interesting ligands for coordination chemistry. Convenient synthetic routes are presented to access their iridium(I), iridium(III), and coinage-metal(I) (Cu, Ag, Au) complexes in good yields by means of dissociation of olefins, deprotonation of precursor salts, and transmetalation from a silver carbene complex Molecular structures and detailed bonding analyses of these complexes are presented.
  • Beilmann-Lehtonen, Ines; Böckelman, Camilla; Mustonen, Harri; Koskensalo, Selja; Hagström, Jaana; Haglund, Caj (2020)
    Colorectal cancer (CRC), the second most common cancer globally, resulted in 881,000 deaths in 2018. Toll-like receptors (TLRs) are crucial to detecting pathogen invasion and inducing the host's immune response. This study aimed to explore the prognostic value of TLR2 and TLR4 tumor expressions in colorectal cancer patients. We studied the immunohistochemical expressions of TLR2 and TLR4 using tissue microarray specimens from 825 patients undergoing surgery in the Department of Surgery, Helsinki University Hospital, between 1982 and 2002. We assessed the relationships between TLR2 and TLR4 expressions and clinicopathological variables and patient survival. We generated survival curves using the Kaplan-Meier method, determining significance with the log-rank test. Among patients with lymph node-positive disease and no distant metastases (Dukes C), a strong TLR2 immunoactivity associated with a better prognosis (p <0.001). Among patients with local Dukes B disease, a strong TLR4 immunoactivity associated with a worse disease-specific survival (DSS; p = 0.017). In the multivariate survival analysis, moderate TLR4 immunoactivity compared with strong TLR4 immunoactivity (hazard ratio (HR) 0.66, 95% confidence interval (CI) 0.49-0.89, p = 0.007) served as an independent prognostic factor. In the multivariate analysis for the Dukes subgroups, moderate TLR2 immunoactivity (HR 2.63, 95% CI 1.56-4.44, p <0.001) compared with strong TLR2 immunoactivity served as an independent negative prognostic factor in the Dukes C subgroup. TLR2 and TLR4 might be new prognostic factors to indicate which CRC patients require adjuvant therapy and which could spare from an unnecessary follow-up, but further investigations are needed.