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European Journal of Inorganic Chemistry

Claudia Heindl, Sabine Reisinger, Christoph Schwarzmaier, Lena Rummel, Alexander V Virovets, Eugenia V Peresypkina, Manfred Scheer
Phosphaferrocenes in combination with coinage metal salts proved to be excellent building blocks in supramolecular chemistry for the buildup of oligomeric and polymeric assemblies. The synthesis of a series of novel phosphaferrocenes containing the 1,3-P2C3 iPr3 and/or the 1,2,4-P3C2 iPr2 ligand is described herein. The self-assembly processes of the 1,3-diphospha-, 1,2,4-triphospha-, and 1,1',2,3',4-pentaphosphaferrocenes with Cu(I) halides led to the formation of 1D or 2D polymers. With [Cp*Fe(η(5)-P2C3 iPr3)] (Cp* = η(5)-C5Me5), infinite chains are formed, whereas with [(η(5)-P3C2 iPr2)Fe(η(5)-P2C3 iPr3)] 1D ladderlike structures are obtained...
February 2016: European Journal of Inorganic Chemistry
Andrew R Jupp, Michael B Geeson, John E McGrady, Jose M Goicoechea
A synthesis of the 2-phosphathioethynolate anion, PCS(-), under ambient conditions is reported. The coordination chemistry of PCO(-), PCS(-) and their nitrogen-containing congeners is also explored. Photolysis of a solution of W(CO)6 in the presence of PCO(-) [or a simple ligand displacement reaction using W(CO)5(MeCN)] affords [W(CO)5(PCO)](-) (1). The cyanate and thiocyanate analogues, [W(CO)5(NCO)](-) (2) and [W(CO)5(NCS)](-) (3), are also synthesised using a similar methodology, allowing for an in-depth study of the bonding properties of this family of related ligands...
February 2016: European Journal of Inorganic Chemistry
Jorge Jimenez, Indranil Chakraborty, Pradip K Mascharak
Four manganese carbonyl complexes of the type [MnBr(CO)3(NˆN)] (NˆN = α-diimine ligands) namely [MnBr(CO)3(bpy)] (1), [MnBr(CO)3(phen)] (2), [MnBr(CO)3(dafo)] (3) and [MnBr(CO)3(pyzphen)] (4) (where bpy = bipyridine, phen = 1,10-phenanthroline, dafo = 4,5-diazafluoren-9-one and pyzphen = pyrazino[2,3-f][1,10]-phenanthroline) have been synthesized and structurally characterized. These four complexes containing the fac-[Mn(CO)3] motif release CO upon illumination with low power visible and UV light. The CO release rates and the absorption maxima of the complexes are however very similar despite systematic increase in structural complexity in the rigid α-diimine ligand frames...
October 2015: European Journal of Inorganic Chemistry
Manuel Kaiser, Günther Knör
The air- and moisture-stable iron-sulfur carbonyl clusters Fe3S2(CO)7(dppm) (1) and Fe3S2(CO)7(dppf) (2) carrying the bisphosphine ligands bis(diphenylphosphanyl)methane (dppm) and 1,1'-bis(diphenylphosphanyl)ferrocene (dppf) were prepared and fully characterized. Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested. The molecular structures of the methylene-bridged compound 1 and the ferrocene-functionalized derivative 2 were determined by single-crystal X-ray diffraction...
September 2015: European Journal of Inorganic Chemistry
Marco Chino, Ornella Maglio, Flavia Nastri, Vincenzo Pavone, William F DeGrado, Angela Lombardi
A single polypeptide chain may provide an astronomical number of conformers. Nature selected only a trivial number of them through evolution, composing an alphabet of scaffolds, that can afford the complete set of chemical reactions needed to support life. These structural templates are so stable that they allow several mutations without disruption of the global folding, even having the ability to bind several exogenous cofactors. With this perspective, metal cofactors play a crucial role in the regulation and catalysis of several processes...
July 2015: European Journal of Inorganic Chemistry
Johannes Kreutzer, Matthias Czakler, Michael Puchberger, Ernst Pittenauer, Ulrich Schubert
Reaction of [Ti4Zr4O6(OBu)4(OMc)16] (OMc = methacrylate) with acetylacetone (acacH) resulted in dissection of the cluster and formation of [Ti(OBu)2(acac)2] and the smaller cluster [Ti2Zr4O4(OMc)16]. In contrast, the same reaction with [Zr6O4(OH)4(OOCR)12]2 ·6RCOOH (R = Et, CH2CH=CH2) led to site-selective substitution of two carboxylate ligands and formation of isostructural [Zr6O4(OH)4(OOCR)12-x (acac) x ]2 ·6RCOOH (x ≤ 1).
June 2015: European Journal of Inorganic Chemistry
Yosra Benabdelouahab, Laura Muñoz-Moreno, Malgorzata Frik, Isabel de la Cueva-Alique, Mohammed Amin El Amrani, María Contel, Ana M Bajo, Tomás Cuenca, Eva Royo
The investigation of the hydrogen-bonding effect on the aggregation tendency of ruthenium compounds [(η(6)-p-cymene)Ru(κNHR,κNOH)Cl]Cl (R = Ph (1a), Bn (1b)) and [(η(6)-p-cymene)Ru(κ(2)NH(2-pic),κNOH)][PF6]2 (1c), [(η(6)-p-cymene)Ru(κNHBn,κNO)Cl] (2b) and [(η(6)-p-cymene)Ru(κNBn,κ(2)NO)] (3b), has been performed by means of concentration dependence (1)H NMR chemical shifts and DOSY experiments. The synthesis and full characterization of new compounds 1c, [(η(6)-p-cymene)Ru(κNPh,κ(2)NO)] (3a) and 3b are also reported...
May 2015: European Journal of Inorganic Chemistry
Johannes Kreutzer, Michael Puchberger, Christine Artner, Ulrich Schubert
The exchange of the carboxylato ligands of Zr4O2(methacrylato)12 in reactions with carboxylic acids proceeds with retention of the composition and structure of the cluster core. This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters. The IR bands were assigned on the basis of DFT calculations. Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters...
April 2015: European Journal of Inorganic Chemistry
Christine Artner, Stefan Kronister, Matthias Czakler, Ulrich Schubert
The mixed-metal oxo clusters LnTi4O3(OiPr)2(OMc)11 (Ln = La, Ce; OMc = methacrylate), Ln2Ti6O6(OMc)18(HOiPr) (Ln = La, Ce, Nd, Sm) and Ln2Ti4O4(OMc)14(HOMc)2 (Ln = Sm, Eu, Gd, Ho) have been synthesized from titanium isopropoxide, the corresponding lanthanide acetate and methacrylic acid. The type of cluster obtained strongly depends on the size of the lanthanide ion.
November 2014: European Journal of Inorganic Chemistry
Christine Artner, Ayse Koyun, Matthias Czakler, Ulrich Schubert
The mixed-metal oxo clusters FeTi5O4(OiPr)4(OMc)10 (OMc = methacrylate), Zn2Ti4O4(OiPr)2(OMc)10, Cd4Ti2O2(OAc)2(OMc)10(HOiPr)2, [Ca2Ti4O4(OAc)2(OMc)10] n , and [Sr2Ti4O4(OMc)12(HOMc)2] n were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid. Their structures are derived from Ti clusters with the composition Ti6O4(OR)8(OOCR')8. The Ca and Sr derivatives consist of chains of condensed clusters.
October 2014: European Journal of Inorganic Chemistry
Tai Lin, Olbelina A Ulloa, Thomas B Rauchfuss, Danielle L Gray
The reaction of Fe3(CO)12 with the dithiadiazacyclooctanes [SCH2N(R)CH2]2 affords Fe2[SCH2N(Me)CH2](CO)6 (R = Me, Bn). The methyl derivative 1(Me) was characterized crystallographically (Fe-Fe = 2.5702(5) Å). Its low symmetry is verified by variable temperature (13)C NMR spectroscopy which revealed that the turnstile rotation of the S(CH2)Fe(CO)3 and S(NMe)Fe(CO)3 centers are subject to very different energy barriers. Although 1(Me) resists protonation, it readily undergoes substitution by tertiary phosphines, first at the S(CH2)Fe(CO)3 center, as verified crystallographically for Fe2[SCH2N(Me)CH2](CO)5(PPh3)...
September 2014: European Journal of Inorganic Chemistry
Denis S Salnikov, Sergei V Makarov, Rudi van Eldik, Polina N Kucherenko, Gerry R Boss
We conducted a detailed kinetic study of the reaction of the vitamin B12 analog diaquacobinamide ((H2O)2Cbi(III)) with hydrogen sulfide in water from pH 3 to 11. The reaction proceeds in three steps: (i) formation of three different complexes between cobinamide and hydrogen sulfide, viz. (HO(-))(HS(-))Cbi(III), (H2O)(HS(-))Cbi(III), and (HS(-))2Cbi(III); (ii) inner-sphere electron transfer (ISET) in the two complexes with one coordinated HS(-) to form the reduced cobinamide complex [(H)S]Cbi(II); and (iii) addition of a second molecule of hydrogen sulfide to the reduced cobinamide...
September 2014: European Journal of Inorganic Chemistry
Matthias Czakler, Christine Artner, Ulrich Schubert
New phosphonate/acetate-substituted titanium oxo/alkoxo clusters were prepared from Ti(OiPr)4 and bis(trimethylsilyl) phosphonates in the presence of acetic acid, which served to generate water in situ through ester formation. The process led to clusters with a higher degree of condensation than in previously known phosphonate-substituted titanium oxo clusters. The clusters [Ti6O4(OiPr)10(OAc)2(O3PR)2] (OAc = acetate) were obtained for a large variety of functional and non-functional groups R under a range of reaction conditions...
April 2014: European Journal of Inorganic Chemistry
Kathrin Wähler, Anja Ludewig, Patrick Szabo, Klaus Harms, Eric Meggers
Rhenium(I) pyridocarbazole complexes with photoinduced antiproliferative activity are reported. The substitutionally inert complexes induce cell death by singlet oxygen generation upon irradiation with red light (λ ≥ 620 nm), while only weak background cytotoxicity is observed in the dark. Due to their ability to inhibit protein kinases (nanomolar IC50 values against Pim1 at 10 μM ATP), this class of rhenium complexes point into the direction of dual function antiproliferative therapy with a single drug in which photodynamic therapy is combined with the inhibition of cancer related protein kinases...
February 1, 2014: European Journal of Inorganic Chemistry
Ernst Hinteregger, Klaus Wurst, Lukas Perfler, Florian Kraus, Hubert Huppertz
A new actinide borate phosphate, U2[BO4][PO4], was synthesized in a Walker-type multianvil apparatus at 12.5 GPa and 1000 °C. The crystal structure was determined from single-crystal X-ray diffraction data collected at room temperature. U2[BO4][PO4] crystallizes in the monoclinic space group P21/c with four formula units per unit cell and the lattice parameters a = 854.6(2), b = 775.3(2), c = 816.3(2) pm, and β = 102.52(3)°. The structure consists of double layers of linked uranium-oxygen polyhedra parallel to [100]...
October 14, 2013: European Journal of Inorganic Chemistry
József S Pap, Matthew A Cranswick, E Balogh-Hergovich, Gábor Baráth, Michel Giorgi, Gregory T Rohde, József Kaizer, Gábor Speier, Lawrence Que
The complex [Fe(indH)(solvent)3](ClO4)2 (1) has been isolated from the reaction of equimolar amounts of 1,3-bis(2'-pyridylimino)isoindoline (indH) and Fe(ClO4)2 in acetonitrile and characterized by X-ray crystallography and several spectroscopic techniques. It is a suitable catalyst for the oxidation of thioanisoles and benzyl alcohols with H2O2 as the oxidant. Hammett correlations and kinetic isotope effect experiments support the involvement of an electrophilic metal-based oxidant. A metastable green species (2) is observed when 1 is reacted with H2O2 at -40 °C, which has been characterized to have a Fe(III)(μ-O)(μ-O2)Fe(III) core on the basis of UV-Vis, electron paramagnetic resonance, resonance Raman, and X-ray absorption spectroscopic data...
August 2013: European Journal of Inorganic Chemistry
Jacqui Tehranchi, Patrick J Donoghue, Christopher J Cramer, William B Tolman
The complexes (Bu4N)(L(Me)M(II)-OH) (L(Me) = 2,6-dimethylphenyl-substituted pyridine(dicarboxamide); M = Cu or Ni) react with CH3CN to yield (Bu4N)(L(Me)M-CH2CN), novel cyanomethide complexes that were fully characterized, including by X-ray crystallography. These conversions contrast with the usual reactions of metal-hydroxide complexes with nitriles, which typically involve attack at the nitrile carbon and formation of amides or carboxylic acids. Kinetic studies (M = Cu) revealed a first-order dependence on the complex and a kinetic isotope effect (k(CH3CN)/k(CD3CN) of 4...
August 1, 2013: European Journal of Inorganic Chemistry
Thomas R Dugan, K Cory Macleod, William W Brennessel, Patrick L Holland
The cooperative binding of N2 by late transition metals and main-group metals is a promising strategy for N-N bond weakening and activation. We report the use of activated Rieke magnesium for reduction of iron and cobalt complexes supported by bulky β-diketiminate ligands. Binding of N2 is accompanied by assembly of a linear M-NN-Mg-NN-M (M = Co, Fe) core with N-N bonds that are weakened, as judged by infrared spectroscopy. Both the cobalt and iron complexes require THF solvent, because of Mg-THF binding. The cobalt complex can be isolated as a pure solid, but the iron complex is stable only in solution...
August 1, 2013: European Journal of Inorganic Chemistry
David T Walker, Rohan S Dassanayake, Kamille A Garcia, Riya Mukherjee, Nicola E Brasch
The essential but also toxic gaseous signaling molecule nitric oxide is scavenged by the reduced vitamin B12 complex cob(II)alamin. The resulting complex, nitroxylcobalamin (NO(-)-Cbl(III)), is rapidly oxidized to nitrocobalamin (NO2Cbl) in the presence of oxygen; however it is unlikely that nitrocobalamin is itself stable in biological systems. Kinetic studies on the reaction between NO2Cbl and the important intracellular antioxidant, glutathione (GSH), are reported. In this study, a reaction pathway is proposed in which the β-axial ligand of NO2Cbl is first substituted by water to give aquacobalamin (H2OCbl(+)), which then reacts further with GSH to form glutathionylcobalamin (GSCbl)...
June 1, 2013: European Journal of Inorganic Chemistry
Rupali Deshmukh, Ulrich Schubert
Copper oxide nanoparticles within hollow mesoporous silica spheres were prepared by binding/adsorbing Cu(2+) or [Cu(NH3)4(H2O)2](2+) ions on the surface of carbon spheres, followed by formation of a mesoporous silica shell by sol-gel processing and calcination in air. The CuO nanoparticles can subsequently be converted into Cu3N nanoparticles by nitridation with ammonia. The effect of the different copper precursors, i.e. Cu(2+) and [Cu(NH3)4(H2O)2](2+), on the nanocomposites was studied. CuO nanoparticles on the outer surface of hollow silica spheres were obtained by thermal treatment of hollow CuSiO3 spheres in air...
May 2013: European Journal of Inorganic Chemistry
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