bluuebunny/crossref_metadata_2025 huggingface dataset:
Ein neues Selten-Erd-Metall(III)-Oxidchlorid-Oxotellurat(IV): Nd5O4Cl3[TeO3]2 / A New Rare Earth-Metal(III) Oxide Chloride Oxotellurate(IV): Nd5O4Cl3[TeO3]2
Authors: Zitzer Sabine , Schleid Thomas
Published: February 2015

Pale violet, plate-like single crystals of the title compound, neodymium(III) oxide chloride oxotellurate( IV) Nd5O4Cl3[TeO3]2, can be obtained by the reaction of Nd2O3 with NdCl3 and TeO2 in equimolar ratios in evacuated silica ampoules within five days at 775 °C with an excess of CsCl added as fluxing agent. Nd5O4Cl3[TeO3]2 crystallizes in the monoclinic space group C2/m (no. 12) with the lattice parameters a = 1270.61(9), b = 562.70(4), c = 1008.97(8) pm, β = 90.784(3)°and Z = 2, and is thus isostructural to the lanthanoid(III) oxide halide oxoselenates(IV) Tb5O4Cl3[SeO3]2 and Gd5O4Br3[SeO3]2. The crystal structure exhibits three crystallographically different Nd3+ cations, of which (Nd1)3+ has a purely oxidic coordination sphere of eight oxide anions building up a square prism. (Nd2)3+ and (Nd3)3+ are both coordinated by oxide and chloride anions. The coordination polyhedron around (Nd2)3+ is a trigonal prism of oxide anions that is capped by one chloride anion to give a coordination number of seven. (Nd3)3+ resides in an eightfold coordination of five oxide and three chloride anions forming a square antiprism. All (O1)2
− anions are surrounded tetrahedrally by Nd3+ cations as [ONd4]10+ units. These tetrahedra share common edges and vertices to generate two-dimensional infinite layers of the composition ∞
2
{[O4Nd5]7+
}, which extend parallel to the (001) plane. The chloride anions (Cl1)
−
are connecting those slabs via Nd3-Cl1-Nd3 bridges along the [001] direction, while the (Cl2)− anions alternate with the Te4+ cations above and below the layers. The three-dimensional crystal structure of Nd5O4Cl3[TeO3]2 is completed by Te4+ cations, which are bonded to one (O2)2
− and two (O3)2
− anions to form ψ1-tetrahedra [TeO3]2
− with a nonbinding, stereochemically active electron pair (“lone pair”) pointing into the free space between the chloride-decorated ∞
2
{[O4Nd5]7+
} layers
Oxokohlenstoffe und verwandte Verbindungen. 33 [1]. Über die Umsetzung von 3-Antipyryl-4-hydroxy-cyclobutendion mit Aminen: Antipyryl-arylamino-quadraine – eine neue Klasse von C,N-Quadrainen / Oxocarbons and Related Compounds. 33 [1]. On the Reaction of 3-Antipyryl-4-hydroxy-cyclobutenedione with Amines: Antipyryl-arylamino-squaraines – a New Class of C,N-Squaraines
Authors: Schmidt Arthur H. , Kohler Jochen , Pretsch Ramona , Freytag-Loringhoven Sarah von , Sohrabnejad-Eskan Iman , Wiesert Peter R.
Published: February 2015

Antipyryl-arylamino-squaraines (11a -w) have been prepared by condensation of 3-antipyryl-4- hydroxy-cyclobutenedione (9a) with the primary aromatic amines 10a -w, using preferentially EtOH as the reaction medium. Surprisingly, 3-antipyryl-4-hydroxy-cyclobutenedione (9a) and 4-aminoantipyrine (13), under similar conditions, yielded 3-antipyryl-4-antipyrylamino-cyclobutenedione (14a), and not the expected squaraine. Reactions of 9a with the o-phenylenediamines 16a and 16b afforded the quinoxalines 17a and 17b, respectively
Phytogrowth Activity of 3-(3-Chlorobenzyl)-5-arylidenefuran-2(5H)-ones
Authors: Barbosa Luiz C.A. , Demuner Antônio J. , Maltha Célia R. A. , Teixeira Róbson R. , Souza Kamilla A. P. , Bicalho Keylla U.
Published: February 2015

Nine new 3-(3-chlorobenzyl)-5-arylidenefuran-2(5H)-ones were prepared in 20 - 87% yields by reaction of 3-(3-chlorobenzyl)furan-2(5H)-one with pertinent aldehydes. All compounds were fully characterized by IR and NMR spectroscopy as well asMS spectrometry. The phytotoxic properties of the synthesized lactones were evaluated as the ability to interfere with the growth of Sorghum bicolor and Cucumis sativus seedlings at 10 ppm and 100 ppm. Lactone 12, at 10 ppm, was the most active and selective, inhibiting the S. bicolor and C. sativus root growth by 70.7% and 10.7%, respectively. At 10 ppm, lactone 14 caused the larger effect on the inhibition (41.9%) of C. sativus. In general, the results indicate the influence of the benzylidene ring substitution on the phytotoxic activity
Beryllium Diammine Difluoride [BeF2(NH3)2]
Authors: Kraus Florian , Fichtl Matthias B. , Baer Sebastian A.
Published: February 2015

Beryllium difluoride BeF2 reacts with liquid ammonia forming discrete diammine difluoro beryllium( II) [BeF2(NH3)2] molecules. The colorless compound crystallizes in the monoclinic space group P21/c with a = 4.8815(2), b = 6.8528(3), c = 10.3690(5) Å, β = 92.01(1)◦, V = 346.65(3) Å3 at 123 K with Z = 4. [BeF2(NH3)2] is the first structurally characterized example of a berylliumammonia complex. The compound has been investigated further by Raman, IR, and DTA-TG measurements and by quantum chemical ELF, AIM and NBO calculations.
Synthesis, Crystal Structure and Electrochemical Properties of a New Adduct of Benzo-15-crown-5 and H3PMo12O40
Authors: Du Qinghua , Song Dawei , You Wansheng , Zhao Yi , Gan Tingting , Dai Limei
Published: February 2015

A new crown ether-POM (POM = polyoxometalate) adduct with the molecular formula [(C14- H20O5)4(H3O)3]PMo12O40 ・ 0.5CH3CN (1) was isolated from the mixed solvent of acetonitrile and methanol. The adduct is constructed from Keggin [PMo12O40]3− anions and [(C14H20O5)- (H3O+)] and [(C14H20O5)2(H3O+)] cations via electrostatic and hydrogen bonding interactions. The supramolecular interactions combine the crown ether with oxonium ions. In the [(C14H20O5)- (H3O+)] moieties, the oxonium ions reside out of the planes defined by the oxygen atoms of the crown ether. The [(C14H20O5)2(H3O+)] moieties exhibit a sandwich structure. There exist hydrogen bonds between the oxonium ions of the [(C14H20O5)(H3O)]+ cations and the acetonitrile molecules and the terminal and bridging oxygen atoms of the [PMo12O40]3− anions. The adduct has been used as a bulk-modifier to fabricate a chemically modified carbon paste electrode (MCPE), which displays well-defined cyclic voltammograms with three reversible two-electron redox couples in acidic aqueous solution, and electrocatalytic activities towards the reduction of H2O2 and NO2−.
On the Reaction of Cyanamides with N-Alkylnitrilium and N,N-Dialkylcyanamidium Salts
Authors: Abu-El-Halawa Rajab
Published: February 2015

N-Alkylnitrilium and N,N-dialkylcyanamidium salts 1 and 2 undergo ene reactions with cyanamides 4 to afford 2-azoniaallene salts 7 and 9 in which the N-alkylnitrilium salts 1 react as the ene, and the cyanamides 4 react as the enophile components. Competing with the ene reaction, N-alkylnitrilium salts 1 undergo [2++2+2] cycloaddition to furnish triazinium salts 8. 2-Azoniaallene salts react with alcohols to afford alkoxy amino derivatives 10 and 12, which yield iminium salts 11 and ketals/acetals upon further reaction with alcohols. The constitution of the 2-azoniaallene 7 and 9 and triazinium salts 8 was secured by elemental analyses and spectral properties (IR and NMR).
Elimination of a Thiomethyl Substituent from an Anionic 5-Methylenebarbituric Acid Derivative by Oxidation and Substitution
Authors: Al-Sheikh Ahmad , Sweidan Kamal , Kuhn Norbert , Maichle-Mößmer Cäcilia , Steimann Manfred
Published: February 2015

Triethylammonium 5-[(1,3-dimethyl-2,4,6-trioxo-tetrahydropyrimidin-5(6H)-ylidene)-(methylthio) methyl]-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate (5), obtained from 5-[bis (methylthio)methylene]-1,3-dimethyl-2,4,6(1H,3H,5H)-pyrimidinetrione (2) and 1,3-dimethylbarbituric acid in the presence of triethylamine, is protonated by methanesulfonic acid to give 5,5ʹ-(methylthiomethanediylidene)bis(1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione) (6) in good yield. Compound 6 is oxidized in two steps by m-chloroperbenzoic acid to give 5,5ʹ- (methylsulfinylmethanediylidene)bis(1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione) (7) and 5-[(1,3-dimethyl-2,4,6-trioxo-tetrahydropyrimidin-5(6H)-ylidene)(methylsulfinyl)methyl]-5-hydroxy- 1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (8), respectively. Excess pyridine eliminates methanesulfinic acid from 8 to give the zwitterionic 5-[(1,3-dimethyl-2,4,6-trioxo-tetrahydropyrimidin- 5(6H)-ylidene(pyridinium-1-yl)methyl]-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin- 4-olate (9). The crystal structures of compounds 6, 8, and 9 are reported.
Short Approach Towards New Isocoumarins and Dihydroisocoumarins and Investigation of their Cytotoxic Activities
Authors: Wetzel Isolde , Bracher Franz , Krauss Jürgen
Published: February 2015

3-Substituted isocoumarins were prepared in a short and efficient way from 2-iodobenzoic acid and terminal alkynes in a one-pot Sonogashira reaction. Catalytic hydrogenation gave the corresponding dihydroisocoumarins. The cytotoxic activities of the resulting compounds against human leukaemia cell line (HL 60) were determined in a MTT assay, and structure-activity relationships are discussed.
Structure and Magnetic Properties of a Single-strand Helical Cobalt(II) Coordination Polymer
Authors: Chen Quan-Li , Wang Xian-Wen , Zhang Yong-Hua , Chen Jing-Zhong
Published: February 2015

The one-dimensional helical chain-like coordination polymer [Co(bpdc)(H2O)3]・H2O (1) has been synthesized by hydrothermal reaction of pdon with Co(NO3)2・6H2O and Na2B4O7 (bpdc = 2,2ʹ-bipyridyl-3,3ʹ-dicarboxylate, pdon = 1,10-phenanthroline-5,6-dione). 1 crystallizes in the monoclinic space group P21/n with the cell parameters: a = 9.987(1), b = 9.238(1), c = 16.080(2) Å, β = 97.471(1)°, V = 1471.0(3) Å3, Z = 4. The bpdc ligand has resulted from an in situ carbon-carbon bond cleavage in the pdon ligand. The Co(II) atom is surrounded by two nitrogen atoms of the bpdc pyridyl groups and four O atoms, of which three belong to coordinated water molecules and one to a bpdc carboxylate group. The six-coordinated Co(II) atom adopts a distorted octahedral geometry. Compound 1 displays antiferromagnetic interactions. Above 30 K, χm −1 obeys the Curie- Weiss law with C = 3.12 cm3 K mol−1 andΘ = −10.6 K.
Magnetic Ordering in CeZnGe
Authors: Hermes Wilfried , Pöttgen Rainer
Published: February 2015

CeZnGe crystallizes with the hexagonal YPtAs-type structure, space group P63/mmc, a = 430.0(2), c = 1678.8(10) pm. A phase-pure sample was synthesized from the elements in a sealed tantalum crucible in a high-frequency furnace. Magnetic susceptibility measurements have revealed a trivalent cerium with an experimental magnetic moment of 2.67(1) μB/Ce atom. Ferromagnetic ordering sets in at TC = 4.6(2) K.
Platinum-Germanium Ordering in the Germanides REPtGe with the Heavy Rare Earth Elements
Authors: Rodewald Ute Ch. , Heying Birgit , Hoffmann Rolf-Dieter , Niepmann Dirk , Pöttgen Rainer
Published: February 2015

The equiatomic germanides REPtGe with the heavy rare earth elements (RE) have been reinvestigated with respect to platinum-germanium ordering. The compounds were prepared by arc-melting of the elements followed by annealing for two weeks at 1070 K. The REPtGe germanides crystallize with the TiNiSi-type structure, space group Pnma. The structures of ErPtGe (a = 692.01(5), b = 432.03(4), c = 753.19(5) pm, wR2 = 0.0523, 435 F2, 20 variables) and the new germanide LuPtGe (a = 683.1(1), b = 429.2(1), c = 750.3(1) pm, wR2 = 0.0696, 358 F2, 20 variables) have been refined from single crystal diffractometer data. These structures exhibit three-dimensional [PtGe] networks with strong Pt-Ge intra- (251 - 255 pm in LuPtGe) and weaker interlayer (272 pm in LuPtGe) interactions. The crystal chemical peculiarities of the whole REPtGe series are briefly discussed.
The Smallest “Aurophilic Species”
Authors: Berger Raphael J. F.
Published: February 2015

The existence of the C2v symmetric closed-shell di[gold(I)]hydronium cation [Au2H]+ (1), is predicted. It is shown that 1 is the smallest possible molecular species containing aurophilic contacts. Equilibrium structural parameters, vibrational frequencies and formation energies of 1 from Au+ and AuH, have been calculated, employing a series of highly correlated but available standard relativistic ab initio methods up to CCSD(T) level of theory and all-electron basis sets of quadruple-ζ quality with double polarizations. Relativistic effects have been taken into account by employing pseudorelativistic electron core potentials (ECP) or a scalar relativistic treatment using a Douglas-Kroll-Heß Hamiltonian of 2nd, 3rd and 4th order (DKH2, DKH3, DKH4).
Synthesis, Crystal Structure and Electrochemical Studies of a Hydrazone Schiff Base Complex of Titanium(IV)
Authors: Monfared Hassan Hosseini , Nazari Majid , Mayer Peter , Kamyabi Mohammad-Ali , Erxleben Andrea , Asgari Zohre
Published: February 2015

The in situ formed hydrazone Schiff base ligand (E)-N´-(2-hydroxy-3-methoxybenzylidene)- benzohydrazide (L2−) reacts with bis(acetylacetonato)titanium(IV) oxide in methanol to a mononuclear [Ti(L)(OCH3)(acac)] complex which crystallizes in the monoclinic space group P21/c, a = 18.2786(13), b = 8.2609(5), c = 13.9008(10) Å , β = 96.809(3)° with Z = 4. Cyclic voltammetric experiments of the species in acetonitrile solution reveals a reversible peak at Eo´ = −0.768 V (vs. Ag/AgCl) relating to the TiIV/TiIII redox process.
A New Cyclooxygenase Inhibitor from Incarvillea arguta
Authors: Tan Qin-Gang , Cai Xiang-Hai , Du Zhi-Zhi , Feng Tao , Luo Xiao-Dong
Published: February 2015

A new anti-inflammatory spirovetivane-type sesquiterpenoid, designated as 1,10-didehydrolubimin (1) and thirteen known compounds (2 - 14) were isolated from the whole plants of the ‘Yi’ ethnomedicinal plant Incarvillea arguta. Their structures were established based on spectral methods and by comparison of the spectral data with those reported previously. Compound 1 exhibited significant inhibitory effects on Cox-1 and Cox-2 and a negative effect against 5-Lox at the concentration of 100 μM.
Two New Clerodane-type Diterpenoids from Gomphostemma microdon
Authors: Zhang Rong-Ting , Feng Tao , Cai Xiang-Hai , Luo Xiao-Dong
Published: February 2015

Two new clerodane-type diterpenoids, along with seven known compounds have been isolated from the aerial parts of Gomphostemma microdon. All structures were established on the basis of spectroscopic analyses, including application of MS, UV, IR, 1D and 2D NMR techniques.
The Lanthanoid Osmium Gallides Er2Os3Ga10 and Tm2Os3Ga10 with Yb2Ru3Ga10-type Structure
Authors: Jeitschko Wolfgang , Schlüter Martin
Published: February 2015

The title compounds were prepared by melting and annealing of stoichiometric mixtures of the elemental components in a high-frequency furnace. They are isotypic with Yb2Ru3Ga10 (P4/mbm, Z = 2). Their lattice constants were determined from X-ray powder data, and their crystal structures were refined from single-crystal X-ray data. Er2Os3Ga10: a = 883.4(1), c = 636.7(1) pm, R = 0.025 for 506 Fo values, and Tm2Os3Ga10: a = 883.2(1), c = 633.6(1) pm, R = 0.023 for 568 Fo values and 25 variable parameters each. The crystal structures of these intermetallic compounds are briefly discussed.
Microwave-assisted Oxidation of 3,4-Dihydropyrimidin-2(1H)-ones
Authors: Memarian Hamid Reza , Sabzyan Hassan , Farhadi Asadollah
Published: February 2015

A new facile cost-effective method for the oxidation of acetyl and carboethoxy derivatives of 3,4- dihydropyrimidin-2(1H)-ones (DHPMs) by using potassium peroxydisulfate in water as solvent under microwave irradiation has been developed. Whereas the presence of the acetyl group instead of the carboethoxy group in position 5 decreases the rate of oxidation, the nature of the additional subtituent (electron-donating or electron-withdrawing group) and its location on the phenyl ring (ortho-, meta- or para-position) attached to C-4 of the dihydropyrimidinone ring influence the rate of reaction. Increase in the rate of the reaction compared with that of the reaction under reflux condition is the advantage of the use of microwave irradiation for this oxidation method.
Facile Synthesis of Non-nucleoside Compounds Starting from α-Chlorocarbenium Ions and Isocyanates as Potential HIV-1 Reverse Transcriptase Inhibitors
Authors: Hamed Atef A. , Zeid Ibrahim F. , Manaa Alaa A.
Published: February 2015

Chloro(phenyl)carbenium hexachloroantimonate salts react with isocyanates to afford either isoindolium (1) or benzoxazinium salts (2). Addition of one equivalent of alcohol to 2 led, after hydrolysis with aq. NaOH, to the formation of benzoxazin-2-ones 3. Treatment with a large excess of alcohol transformed the salts 1 and 2 to the corresponding isoindol-1-ones 11 and the isocyanates 5, respectively. Reaction of 5 with primary amines furnished the urea derivatives 6 in good yield. The biological activity of 6a - o against HIV-1 was determined.
Synthesis and Spectroscopic Characterization of Mixed Diamidophosphoric Acid Esters: X-Ray Crystal Structure of [(CH3)2N]-[p-H3C-C6H4-O]P(O)X (X = NHC(CH3)3 and p-H3C-C6H4-NH)
Authors: Ghadimi Saied , Pourayoubi Mehrdad , Ebrahimi Valmoozi Ali Asghar
Published: February 2015

Mixed diamidophosphoric acid esters [(CH3)2N][p-H3C-C6H4-O]P(O)X, where X = NH(CH3) (1), NHCH(CH3)2 (2), NHC(CH3)3 (3) and p-H3C-C6H4-NH (4) were synthesized and characterized by 31P, 31P{1H}, 13C, 1H NMR, and IR spectroscopy and mass spectrometry, and single crystal X-ray diffraction analysis for the compounds 3 and 4. Compound 3 crystallizes in the monoclinic, space group P21/c with unit cell parameters a = 9.006(3), b = 16.286(5), c = 10.319(3) A° , β = 99.633(6)◦, V = 1492.2(8) °A3, Z = 4. The final R value is 0.0622 for 2074 reflections [I ≥ 2σ (I)]. Compound 4 crystallizes in the orthorhombic, space group Pna21 with unit cell parameters a = 7.0459(14), b = 20.934(4), c = 10.436(2) ° A, V = 1539.3(5) °A3, Z = 4. The final R value is 0.0530 for 3025 reflections [I ≥ 2σ (I)].
Polymorphism in the Germanides REPdGe with the Heavy Rare Earth Elements
Authors: Rodewald Ute Ch. , Heying Birgit , Hoffmann Rolf-Dieter , Niepmann Dirk , Pöttgen Rainer
Published: February 2015

The structures of the equiatomic germanides REPdGe with the heavy rare earth elements have been reinvestigated with respect to palladium-germanium ordering. The samples were prepared by arc-melting of the elements followed by annealing procedures in sealed silica ampoules at different temperatures. The structures of YPdGe, HT-TbPdGe, LT-DyPdGe, HT-DyPdGe, LT-HoPdGe, HT-HoPdGe, ErPdGe, and TmPdGe, and of the new germanide LuPdGe, were refined from single crystal diffractometer data. LT-DyPdGe and LT-HoPdGe crystallize with the YPdSi-type structure, space group Pmmn. The other germanides crystallize with the non-centrosymmetric YbAuSn structure, space group Imm2. All structures are orthorhombically-distorted superstructure variants of AlB2, and they show strong intralayer Pd-Ge bonding within the ordered Pd3Ge3 hexagons. There is weak Pd-Ge and Pd-Pd interlayer bonding. The crystal chemical relationship between the different superstructures is discussed.
Anellation and Ring Transformations of Push-pull-functionalized Deoxypyranosiduloses
Authors: Kordian Marcus , Feist Holger , Peseke Klaus
Published: February 2015

Reaction of (E)-3-aminomethylene-α-D-erythro-hexopyranosid-2-ulose 5 with substituted 5- aminopyrazoles afforded the pyrano-anellated pyrazolo[1,5-a]pyrimidines 8. The treatment of the corresponding (E)-2-aminomethylene-α-D-erythro-hexopyranosid-3-ulose 6 with 5-aminopyrazoles and (benzimidazol-2-yl)acetonitrile yielded in a ring transformation process the D-erythronoyl-pyrazolo[ 1,5-a]pyrimidine-3-carbonic acid derivatives 10 and D-erythronoyl-pyrido[1,2-a]benzimidazole- 4-carbonitrile (12), respectively
Butadiynyl-bridged Diphenothiazines – Redox-active Fluorophores and Self-assembly on HOPG
Authors: Barkschat Christa S. , Guckenberger Reinhard , Müllera Thomas J. J.
Published: February 2015

Ethynyl phenothiazines are oxidatively coupled to symmetrical dumbbell-shaped butadiynylbridged diphenothiazines in good yields. These molecules show intense absorption bands, intense blue-green luminescence with large Stokes shifts, and reversible oxidation potentials in the anodic region. Thermally, these butadiynes do not undergo topochemical polymerization, but oligomerizations to oligomeric polycyclic heterocycles with complex structures in the melt. STM images of two representatives on HOPG (highly oriented pyrolytic graphite) show the formation of monolayers adsorbed by attractive π-π interactions.
Synthesis of 1,4-Diamino-2,3-di(2-pyridyl)butane and its Dinuclear Zinc(II) Chloride Complex
Authors: Kloubert Tobias , Schulz Martin , Görls Helman , Friedrich Manfred , Westerhausen Matthias
Published: February 2015

In a Henry-type reaction nitromethane reacts with N-(2-pyridylmethylidene)-methylamine (1) yielding 1-methylamino-1-(2-pyridyl)-2-nitromethane (2) in nearly quantitative yield. This orange compound decomposes slowly in an inert gas atmosphere and fast in contact with air. Therefore 2 has to be stored at −78 ◦C as a methanol solution. Reduction of 2 with hydrogen in the presence of a Pd/C catalyst leads to the formation of 1,4-dinitro-2,3-di(2-pyridyl)butane (3) in the rather poor yield of 12 %. The major product is the meso-isomer, meso-3, whereas only traces of (R,R)- and (S,S)- isomers of 3 are formed. A conversion of the nitro groups into amino functionalities succeeds with hydrazine hydrate in the presence of a Pd/C catalyst yielding meso-1,4-diamino-2,3-di(2-pyridyl)butane (4). Recrystallization from an aqueous solution gives 4・2H2O. The zinc(II) chloride complex 5 with the metal atoms in distorted tetrahedral environments can be isolated after addition of two equivalents of ZnCl2 to 4. The molecular structures of trimeric 1, meso-3, (R,R)/(S,S)-3, meso-4, and 5 have been determined and are discussed.
A New Aspect of the Pfitzinger Reaction: Microwave-assisted Synthesis of the New Heterocyclic Ring System 6-Arylbenzo[4,5]imidazolo[2,1-b]quino[4,3-e]-1,3-thiazin-14-one
Authors: Abdel-Aziz Hatem A. , Gomha Sobhi M.
Published: February 2015

We report herein on the utility of the Pfitzinger reaction in a facile two-step synthesis of the new heterocyclic ring system 6-arylbenzo[4,5]imidazolo[2,1-b]quino[4,3-e]-1,3-thiazin-14-one using microwave irradiation (MWI) and/or conventional heating. Microwave irradiation was used for a rapid and efficient synthesis of quinoline-4-carboxylic acids 6a - d from the reaction of isatin with 2-(1Hbenzimidazol- 2-ylthio)-1-arylethanones 3a - d. Cyclization of cinchoninic acids 6a - d afforded the fused title compounds 7a - d.
Synthesis of Novel Substituted Dibenzonaphthyridines
Authors: Manoj Manickam , Prasad Karnam J. R.
Published: February 2015

4-Chloro-2-methylquinolines 1a-d on reaction with p-toluidine afforded 2,4’-dimethyl-4-(N-phenylamino) quinolines 2a-d which on reaction with aliphatic and aromatic carboxylic acids yielded the respective 7-substituted dibenzonaphthyridines 3a-d and 4a- d whereas a heterocyclic acid afforded 5a-c and 6a-c.
Two New Isoquinoline Alkaloids from Litsea cubeba
Authors: Feng Tao , Zhang Rong-Ting , Tan Qin-Gang , Liu Ya-Ping , Cai Xiang-Hai , Luo Xiao-Dong
Published: February 2015

Two new aporphine-type isoquinoline alkaloids, (+)-N-(methoxy-carbonyl)-N-norlauroscholtzine (1) and (+)-N-(methoxy-carbonyl)-N-norglaucine (2), were isolated from Litsea cubeba and identified by spectroscopic techniques (NMR, MS, UV, and IR). Their structures contain an N-(methoxycarbonyl) moiety, which has seldomly been found in the natural products of these analogs. Both compounds 1 and 2 showed no antibacterial activity against Staphylococcus aureus.
The First Total Synthesis of Racemic Hydroxymoloka’iamine
Authors: Ullah Nisar
Published: February 2015

The first total synthesis of racemic hydroxymoloka’iamine, a new brominated metabolite isolated from Red Sea sponge Pseudoceratna arabica, was achieved in a high-yield reaction sequence.
Ag13I4(AsO4)3: Synthesis, Crystal Structure and Ionic Conductivity
Authors: Pitzschke Dragan , Curda Jan , Jansen Martin
Published: February 2015

Ruby-red single crystals of Ag13I4(AsO4)3 were prepared for the first time by reacting a stoichiometric mixture of Ag2O, AgI and As2O3 at elevated oxygen pressure of 120 MPa and at a temperature of 350 ◦C. The polyhedral crystals belong to the monoclinic space group P21/m with a = 9.247(1), b = 7.152(1), c = 17.674(2) Å , β = 91.492(2)◦, and Z = 2. The structure is fully ordered and was solved by Direct Methods, and refined on single crystal diffraction data (10376 observed reflections, R1 = 3.28 %). The crystal structure is built up of two two-dimensional interlocked partial structures, one consisting of silver and iodine ions, the other of silver and arsenate(V) ions. The slabs extend in the ac plane, and the Ag-I framework is linked to the AsO4
3− units by Ag-O contacts. The silver-oxygen interactions perturb the tetrahedron of the arsenate group, resulting in As-O distances ranging from 1.670 to 1.697 Å, and angles varying from 107.3 to 112.1◦. Pure Ag13I4(AsO4)3 is a solid ion conductor with a r. t. conductivity of 6.4×10−6 Ω−1 cm−1 at 30 ◦C. The activation energy for silver ion conduction is 0.41 eV in the temperature range from 30 to 130 ◦C
Non-centrosymmetric Ce3OCl[AsO3]2
Authors: Yahia Hamdi Ben , Rodewald Ute Ch. , Pöttgen Rainer
Published: February 2015

The arsenite chloride Ce3OCl[AsO3]2 was synthesized in the form of colorless crystals from arsenic and cerium dioxide in a NaCl / KCl flux at 850 ◦C. Ce3OCl[AsO3]2 crystallizes with the noncentrosymmetric tetragonal Gd3OCl[AsO3]2 type, space group P42nm. The structure was refined from single crystal diffractometer data: a = 12.8590(6), c = 5.5627(3) Å, wR2 = 0.0429, 1463 F2 values, and 65 variables. The structure is built up from chains of trans edge-sharing OCe4/2 tetrahedra. The [AsO3]3− units coordinate to these chains via the oxygen atoms. Their lone-pairs point all to a common channel. Formation of the non-centrosymmetric superstructure is most likely driven by geometrical constraints and is discussed on the basis of a group-subgroup scheme
Crystal Structure of the New Ternary Antimonide Ho5GaSb3
Authors: Antonyshyn Iryna , Zhak Olga , Oryshchyn Stepan , Babizhetskyy Volodymyr , Hoch Constantin , Aksel’rud Lev
Published: February 2015

The crystal structure of the new ternary antimonide Ho5GaSb3 has been determined from X-ray single-crystal data: space group Pnma, a = 7.9667(8), b = 15.128(2), c = 7.9616(8) Å , V = 959.5(3) Å3, Z = 4, RF = 0.059, Rw = 0.066 for 9020 reflections. The crystal structure of Ho5GaSb3 is a ternary derivative of the Sm5Ge4 structure type with partially ordered distribution of gallium and antimony atoms
Ionic Liquid-assisted Solvothermal Synthesis of Ni Particles and Study of Their Electrocatalytic Effect for Calcium Dobesilate Oxidation
Authors: Meng Xiangli , Zhang Shengmao , Xu Hui , Liu Kuaizhi , Wu Zhishen , Zhang Zhijun
Published: February 2015

Graphical Abstract

Ionic Liquid-assisted Solvothermal Synthesis of Ni Particles and Study of Their Electrocatalytic Effect for Calcium Dobesilate Oxidation
Polysulfonylamine, CLXXXVII [1]. Strukturvielfalt in (Acetonitril)silber(I)-di(arensulfonyl)amiden: Zwei Molek¨ulkristalle mit Z'= 1, ein Ionenkristall mit Z' = 2 und zwei auf Halogenbr¨ucken C–Br···O=S beruhende molekulare Polymorphe mit Z' = 1 beziehungsweise Z' = 2 in der gleichen Raumgruppe / Polysulfonylamines, CLXXXVII. Structural Diversity in (Acetonitrile)silver(I) Di(arenesulfonyl)- amides: Two Molecular Z' = 1 Crystals, an Ionic Z' = 2 Crystal, and Two Molecular Polymorphs Based upon C–Br· · ·O=S Halogen Bonds and Featuring Z' = 1 or Z' = 2 in the Same Space Group
Authors: Wölper Christoph , Rodríguez-Gimeno Alejandra , Iborra Katherine Chulvi , Kuhn Helene , Lüttig Anne Kristin , Moll Sabrina , Most Christin , Freytag Matthias , Dix Ina , Jones Peter G. , Blaschette Armand
Published: February 2015

Crystallization of silver di(4-methylbenzenesulfonyl)amide [Ag(MA)], silver di(4-nitrobenzenesulfonyl) amide [Ag(NA)], silver di(4-bromobenzenesulfonyl)amide [Ag(BA)] or silver di(4-fluorobenzenesulfonyl) amide [Ag(FA)] from acetonitrile solutions under slightly different conditions afforded single crystals of the following complexes, which were structurally authenticated by X-ray diffraction at low temperatures: (MeCN)Ag(MA) (1, triclinic, space group P1, Z’ = 1), (MeCN)2Ag(NA) (2, monoclinic, P21/c, Z’ = 1), (MeCN)2Ag(BA) (3, monoclinic, P21/c, Z’ = 1), (MeCN)2Ag(BA) (4, monoclinic, P21/c, Z’ = 2), and [(MeCN)3Ag][Ag(FA)2]・MeCN (5, triclinic , Z’ = 1). In each structure, the inner coordination sphere of silver is formed by the ligand nitrogen atoms, leading to a linear NAgN core for the molecular complex 1 and the complex anion of 5, or to a trigonal planar AgN3 core for the molecular complex 2, the molecular polymorphs 3 and 4, and the complex cation of 5. The flexible di(arenesulfonyl)amide ligands adopt extended pseudo-C2 symmetric conformations in 1, 2 and 5, but folded pseudo-mirror symmetric conformations in 3 and 4. The molecules of 1 are associated into inversion-symmetric dimers via a short Ag・ ・ ・O contact; the dimers form stacks by translation along the a axis, causing the silver ions to segregate in zigzag chains. The arrangement of the molecules in 2 is controlled mainly by a centered C-H・ ・ ・Ph hydrogen bond, a dipolar nitro-nitro and a dipolar nitro-sulfonyl interaction, giving rise to layers oriented parallel to the bc plane. The packing motifs of polymorphs 3 and 4 are very similar. Both forms consist of layers in which the molecules act as 4-connecting nodes in a network based upon C-Br・ ・ ・O=S halogen bonds. In the Z’ = 1 structure of 3, the layers are generated by 2l screw axes and display one short and one long halogen bond, whereas in the Z’ = 2 structure of 4, the layers are realized by glide planes and are based on four independent halogen bonds that are all reasonably short. The packing of 5 exhibits alternating layers comprised of complex anions or of complex cations and acetonitrile solvent molecules, respectively. This Z’ = 2 structure may be viewed as a kinetic polymorph of a more symmetric Z’ = 1 crystal
Synthesis and Characterization of Lead(II) Complexes with the 4-Methoxybenzoyltrifluoroacetonate Ligand
Authors: Marandi Farzin , Krautscheid Harald
Published: February 2015

To investigate the intermolecular interactions of ligands in lead(II) complexes featuring stereochemical activity of the lone electron pair and noncovalent donor-acceptor interactions giving rise also to multidimensional networks, the compounds [Pb2(phen)2(mbtfa)4] (1) and [Pb2(dmp)2 (mbtfa)4] (2) (phen, dmp and mbtfa− for 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline and 4-methoxybenzoyltrifluoroacetonate ligands, respectively) have been prepared and characterized by elemental analysis and their crystal structures investigated. The structures show the coordination number of Pb(II) to be seven and eight, respectively. Supramolecular structures of 1 and 2 are realized by weak directional intermolecular interactions.
Two New Metabolites from Basidiomycete Sparassis crispa
Authors: Jiang Meng-Yuan , Zhang Ling , Dong Ze-Jun , Liu Ji-Kai
Published: February 2015

Two new metabolites, named crispacolide (1) and 3-acetyl-4-hydroxymethyl-tetrahydrofuran (2), were isolated from the fruiting bodies of basidiomycete Sparassis crispa (Wulf.) Fr. The structures and stereochemistry were established on the basis of spectroscopic means
Nickel-deficient Stannides Eu2Ni2–xSn5 – Structure, Magnetic Properties, and Mössbauer Spectroscopic Characterization
Authors: Harmening Thomas , Eul Matthias , Pöttgen Rainer
Published: February 2015

New nickel-deficient stannides Eu2Ni2−xSn5 were synthesized by induction melting of the elements in sealed tantalum tubes. The solid solution was studied by X-ray powder diffraction and two crystal structures were refined on the basis of X-ray diffractometer data: Cmcm, a = 466.03(4), b = 3843.1(8), c = 462.92(9) pm, wR2 = 0.0469, 692 F2 values, 39 variables for Eu2Ni1.49(1)Sn5 and a = 466.11(9), b = 3820.1(8), c = 462.51(9) pm, wR2 = 0.0358, 695 F2 values, 39 variables for Eu2Ni1.35(1)Sn5. This new structure type can be considered as an intergrowth structure of CaBe2Ge2- and CrB-related slabs. The striking structural motifs are nickel-centered square pyramids which are condensed via common corners and edges. The layers of condensed NiSn5 units are separated by the europium atoms. The Ni1 sites within the CaBe2Ge2 slabs show significant defects which leads to split positions for one tin site. Eu2Ni1.50Sn5 shows Curie-Weiss behavior and an experimental magnetic moment of 7.74(1) μB / Eu atom, indicating stable divalent europium, as is also evident from 151Eu Mössbauer spectra. Antiferromagnetic ordering is detected at 3.5 K.
A Systematic Investigation of the Stability Field of Spinel-type Gallium Oxonitrides
Authors: Hering Stefanie A. , Zvoriste Carmen E. , Riedel Ralf , Kinski Isabel , Huppertz Hubert
Published: February 2015

Over the last years, the synthesis and characterization of new spinel-type gallium oxonitrides were in the focus of several working groups. Our systematic investigation of the formation of the gallium oxonitride spinel phases was done under different experimental conditions and with various educts already used in former studies. The experiments took place under high-pressure/high-temperature conditions in a multianvil apparatus, starting from the end members wurtzite-structured GaN and β -Ga2O3. Beside the variation of the molar ratio of the educts (w-GaN:β -Ga2O3 = 9 :1 - 1: 9), different pressures (1 - 11.5 GPa), temperatures (500 - 1350 °C), and heating protocols were studied to localize the formation area of the spinel-type gallium oxonitrides. From these results, initial conditions of 2.5 - 11.5 GPa at temperatures between 1000 - 1300 ◦C can be stated as leading to the formation of cubic, spinel-type gallium oxonitride phases. The temperature stability of the gallium oxonitride spinel phase as well as new results of the transformation of β -Ga2O3 into α-Ga2O3 are reported.
Synthesis and Structures of Silver(I) Adducts with 4-Amino-4H-1,2,4-triazole
Authors: Wang Qiao-Li , Xu Hong , Hou Hong-Wei , Yang Guang
Published: February 2015

Reactions of silver(I) salts with 4-amino-4H-1,2,4-triazole (4-NH2-tz) in a 1 : 1 molar ratio yield four new silver adducts, namely [Ag(4-NH2-tz)](CF3SO3) (1), [Ag(4-NH2-tz)1.75](ClO4) (2), [Ag(4- NH2-tz)1.75](BF4) (3) and [Ag(4-NH2-tz)1.75](NO3) (4). X-Ray analysis shows that 1 exhibits a 3D cationic [Ag(4-NH2-tz)]+ metal-organic framework of srs topology; 2, 3 and 4 are isostructural and display an infinite chain structure containing an Ag4tz6 cluster.
Nucleophilic Aromatic Substitution with 2,3-Dihydro-1,3-diisopropyl- 4,5-dimethylimidazol-2-ylidene
Authors: Mallah Eyad , Kuhn Norbert , Maichle-Mößmer Cäcilia , Steimann Manfred , Ströbele Markus , Zeller Klaus-Peter
Published: February 2015

2,3-Dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (1) reacts with an excess of hexafluorobenzene in the presence of boron trifluoride diethyletherate to give 1,3-diisopropyl-4,5- dimethyl-2-(perfluorophenyl)imidazolium tetrafluoroborate (2). Solutions of 2 exhibit an equilibrium consisting also of hexafluorobenzene and 2,2ʹ-(perfluoro-1,4-phenylene)bis(1,3-diisopropyl- 4,5-dimethylimidazolium)bis(tetrafluoroborate) (3) which is obtained from 1 and hexafluorobenzene in the ratio 2 : 1 on a preparative scale. Similar to 2, 2-(4-cyano-2,3,5,6-tetrafluorophenyl)-1,3- diisopropyl-4,5-dimethylimidazolium tetrafluoroborate (4), 2-(2,4-dicyano-2,5,6-trifluorophenyl)- 1,3-diisopropyl-4,5-dimethylimidazolium tetrafluoroborate (5), and 2-(4,6-difluoro-1,3,5-triazin-2- yl)-1,3-diisopropyl-4,5-dimethylimidazolium tetrafluoroborate (6) are obtained from 1 and perfluorobenzonitrile, 1,3-dicyano-2,4,5,6-tetrafluorobenzene, and 2,4,6-trifluoro-1,3,5-triazin, respectively. The FAB mass spectra of compounds 2 - 6 and the results of the crystal structure analyses of compounds 2 - 4 are discussed.
Mesomorphic Donor-Acceptor-substituted 1,4-Distyrylbenzenes
Authors: Lifka Thorsten , Kalbitz Helga , Meier Herbert
Published: February 2015

The (E,E)-distyrylbenzenes 1a, b with terminal donor-acceptor substitution were prepared by a sequence of four reaction steps including two Wittig-Horner reactions. The products form smectic mesophases, are photostable, and should permit an electric orientation/reorientation, because of their strong dipole character.
Metal Complexes of Biologically Important Ligands, CLXXII [1]. Metal Ions and Metal Complexes as Protective Groups of Amino Acids and Peptides – Reactions at Coordinated Amino Acids
Authors: Beck Wolfgang
Published: February 2015

The introduction of protective groups into multifunctional molecules, e. g. into amino acids for peptide synthesis, and their removal are one of the most important techniques and strategies in Organic Chemistry [2]. Amino acids, their anions and derivatives are versatile ligands, and the leading idea to protect the N- or C-terminus of amino acids by metal ions or by metal complexes has opened interesting chapters which reach from classical coordination and bioinorganic chemistry to modern organometallic and bioorganometallic chemistry [3]
Sn9
4– Zintl Ions as Reactive Precursor for Neat Solids: Syntheses and Crystal Structures of Rb4[SnTe4], KxCs4–x[SnTe4], and KxCs10–x[Sn4Te12]
Authors: Wang Jian-Qiang , Hlukhyy Viktor , Fässler Thomas F.
Published: February 2015

The reactions of Zintl ions Sn9
4− formed in ethylenediamine solutions of K2Cs2Sn9 and Rb4Sn9 with elemental tellurium have been investigated. Addition of elemental tellurium to the filtrates of these solutions leads - depending on the reaction conditions - to four different products: Compounds K0.36(1)Cs3.64(1)[SnTe4] (1) and Rb4[SnTe4] (2) contain the tetrahedral anion [SnTe4]4−, and Cs4[Sn2Te7] (3) features the anion [Te2Sn(μ-Te)(μ-Te2)SnTe2]4−, whereas a novel Zintl anion [Sn4Te12]10− is present in compound K0.44(1)Cs9.56(1)[Sn4Te12] (4). Compounds 1, 2 and 4 have been structurally characterized by single-crystal X-ray diffraction
Cs3NdSi8O19 und Cs6Nd2Si21O48: Zwei cäsiumhaltige Oxosilicate des Neodyms im Vergleich / Cs3NdSi8O19 and Cs6Nd2Si21O48: Two Caesium-containing Oxosilicates of Neodymium in Comparison
Authors: Schäfer Marion C. , Schleid Thomas
Published: February 2015

In the quaternary system Cs / Nd / Si / O, two new representatives, the phyllo-oxosilicate Cs3NdSi8O19 and the tecto-oxosilicate Cs6Nd2Si21O48, were synthesized by CsF-flux-supported solid-state reactions between Nd2O3 and SiO2. The first one, Cs3NdSi8O19 (orthorhombic, Cmcm (no. 63), a = 705.74(5), b = 2712.85(19), c = 1163.72(8) pm, Z = 4), is not isotypic to the related scandium compound Cs3ScSi8O19. The [SiO4]4− tetrahedra (d(Si4+ -O2−) = 156 -163 pm) in the structure of Cs3NdSi8O19 are connected via common corners to form corrugated, loop-branched double layers containing four- and eight-membered rings in the (010) plane and eight-membered rings along [001]. Each of the eight-membered ellipses emerging along [100] is additionally loopbranched by two four-membered chains. The oxosilicate double layers are cross-linked by vertexsharing via otherwise isolated [NdO6]9− octahedra (d(Nd3+-O2-)= 232 - 234 pm) to build up a three-dimensional framework. Also in between the oxosilicate double layers, the (Cs1)+ cations are located on the 8 f site. Each of the octagonal channels along [001] hosts one (Cs3)+ and two (Cs2)+ cations, which both reside at only partially occupied sites (8g and 8 f , respectively) and disorder, because otherwise too short Cs+ ・ ・ ・ Cs+ distances would occur. The second compound, Cs6Nd2Si21O48, crystallizes also in an orthorhombic space group (Pmmn (no. 59), a = 2189.24(15), b = 731.92(5), c = 1593.61(11) pm, Z = 2). Starting from a loop-branched single layer containing five- and eight-membered rings, a three-dimensional framework of vertex-shared [SiO4]4− tetrahedra (d(Si4+-O2−) = 149 - 164 pm) built up, in which the Si-O distances range from 149 to 164 pm within a broad range. In certain cavities, one kind of Nd3+, but four kinds of Cs+ cations (here, all sites with full occupation) are embedded. Also surrounded by only six O2− anions just like in the first case, the Nd3+ cations (d(Nd3+-O2−) = 233 - 237 pm) exhibit an unusually small, but not unknown coordination sphere for this relatively large lanthanoid(III) cation
High-pressure Synthesis and Crystal Structure of the Borate Sc3B5O12
Authors: Neumair Stephanie C. , Huppertz Hubert
Published: February 2015

The rare-earth borate Sc3B5O12 was synthesized under high-pressure / high-temperature conditions of 6 GPa and 1100 °C in a Walker-type multianvil apparatus. The single-crystal structure determination revealed an isotypy to RE3B5O12 (RE = Er-Lu). Sc3B5O12 crystallizes in the rare space group Pmna (Z = 4) with the parameters a = 1245.4(3), b = 443.46(9), c = 1222.1(2) pm, V = 0.675(1) nm3, R1 = 0.0520, and wR2 = 0.0860 (all data). The structure of Sc3B5O12 is composed of layers of condensed BO4 tetrahedra, separated by eight-fold coordinated scandium ions
Synthesis and Properties of 2-(Dimesitylboryl)benzylideneamines
Authors: García-Hernández Zureima , Gabbaï François P.
Published: February 2015

Lithiation of 2-(2-bromophenyl)-dioxolane (1) followed by reaction with dimesitylboron fluoride afforded 2-(2-dimesitylborylphenyl)-dioxolane (2) which was deprotected to afford 2- dimesitylboryl-benzaldehyde (3). Compound 3 reacts with aliphatic amines such as n-butylamine and ethanolamine to afford the corresponding imines 2-(dimesitylboryl)benzylidenebutylamine (4) and 2-(dimesitylboryl)benzylideneethanolamine (5), respectively. Structural studies indicate coordination of the imine-nitrogen atom to the boron center. Imines 4 and 5 emit a green fluorescence near 510 nm with quantum yields approaching 10%. TD-DFT calculations suggest that this emission arises from an intramolecular charge-transfer excited state
Synthesis and Characterization of [3]Ferrocenophane-derived P, P-Chelate Ligand Gold Complexes Featuring an Aurophilic Interaction
Authors: Lübbe Gerrit , Nilewski Christian , Kehr Gerald , Fröhlich Roland , Erker Gerhard
Published: February 2015

The P,P-chelate ligand (rac)-4 was prepared starting from the α-dimethylamino-[3]ferrocenophane by a series of directed ortho-lithiation, phosphination with ClPPh2 and substituent exchange using HPiPr2. Treatment with two molar equivalents of (Me2S)AuCl subsequently gave the corresponding κP,κP(AuCl)2 complex (rac)-9. In similar sequences the α-PCy2/o-PPh2 ligands (S,S,Spl )- 2 and the "substituent-invertomer" (R,R,Rpl)-3 (α-PPh2/o-PCy2) were prepared. Treatment with (Me2S)AuCl in a 1 : 2 ratio gave the chelate ligand-(AuCl)2 complexes (S,S,Spl )-8 and (R,R,Rpl)- 11, respectively. The ligand (rac)-4 and the gold complexes 8, 9 and 11 were characterized by X-ray diffraction. All three show an intramolecular Au . . . Au interaction
Synthetic Access to a Novel Binaphthyl Ligand Bearing a Phosphine and a Triazole Donor Site
Authors: May Claudia , Sun Yu , Wolmershäuser Gotthelf , Thiel Werner R.
Published: February 2015

The combination of a diphenylphospinyl and a triazol-3-yl unit was realized for the first time at a 1,1'-binaphthyl backbone. This novel type of P,N-ligand is accessible as an enantiomerically pure compound in just a few steps. First experiments on the coordination chemistry with palladium(II) chloride have been carried out. A series of intermediates and a binuclear palladium(II) complex could be characterized by X-ray crystal structure analysis
Silver and Gold Complexes with Benzimidazolin-2-ylidene Ligands
Authors: Jahnke Mareike C. , Paley Jennifer , Hupka Florian , Weigand Jan J. , Hahn F. Ekkehardt
Published: February 2015

The dicarbene silver complexes 1a, b of the type [Ag(NHC)2][AgBr2] (NHC = N,N'-dialkylbenzimidazolin- 2-ylidene) have been prepared from the parent benzimidazolium salts by reaction with silver oxide. The silver complexes have been used for the transfer of the carbene ligand to gold(I) giving the gold complexes [AuCl(NHC)] 2a, b in good yields. Crystals of 2a, b have been obtained from chloroform/pentane solutions, and X-ray diffraction structure analyses revealed gold(I) atoms coordinated in a linear fashion by an NHC carbon atom and a chloro ligand
Complexes of Gold(I) with a Chiral Diphosphine Ligand: A Polymer with Both Au···Ag and Ag···Ag Metallophilic Bonds
Authors: Wheaton Craig A. , Jennings Michael C. , Puddephatt Richard J.
Published: February 2015

The chemistry of gold(I) with the ligand binap = 2,2'-bis(diphenylphosphino)-1,1' -binaphthyl is reported. Reaction of [Au2Cl2(μ-binap)] with silver trifluoroacetate gave the corresponding complex [Au2(O2CCF3)2(μ-binap)], and crystallization in the presence of excess silver trifluoroacetate gave the unusual syndiotactic polymeric complex [{Au2Ag2(μ-O2CCF3)4(μ-binap)}n], which contains both Au・ ・ ・Ag and Ag・ ・ ・Ag metallophilic bonds. The trifluoroacetate ligands in [Au2(O2CCF3)2(μ- binap)] can be replaced by nitrogen or phosphorus donor ligands to give complexes [Au2(κ1-4,4'- bipyridine)2(μ-binap)](CF3CO2)2 or meso-[Au2(μ-binap)2](CF3CO2)2
An Octanuclear Gold(I) Cube with Amidinate Ligands Containing Two Hyper-coordinate Ylide Carbon Atoms
Authors: Melgarejo Doris Y. , Chiarella Gina M. , Mohamed Ahmed A. , Fackler John P.
Published: February 2015

Disparate properties of gold(I) converge to produce the first known cube assembly of eight Au(I) atoms connected by four N-bridging amidinate ligands on the sides of the cube, capped above and below by hyper-coordinate carbon atoms from a phosphorous ylide. There are no phosphines coordinated to the Au(I) atoms. The cluster is formulated as [Au8{CH(NC8H9)2}4{(η5- C)P(C6H5)2(CH3)}2]. It displays a strong green luminescence under UV light. The novel product was generated in an attempt to produce luminescent species of gold(I) with mixed C- and Ncoordination, an arrangement not abundant in the literature. The formation and structure of this cluster is reported
Vapochromism in Complexes of Stoichiometry [Au2Ag2R4L2]n
Authors: Fernández Eduardo J. , Laguna Antonio , López-de-Luzuriaga José M. , Olmos M. Elena , Puelles Raquel C.
Published: February 2015

Reaction of [NBu4][Au(C6X5)2] (C6X5 = 3,5-C6Cl2F3, C6Cl5) with AgOClO3 in an Et2O/CH2Cl2 mixture affords [Au2Ag2(C6X5)4(OEt2)2]n [C6X5 = 3,5-C6Cl2F3 (1a), C6Cl5 (1b)]. These compounds react with tetrahydrofuran, acetone, acetonitrile or toluene in solution and in the gas phase (with toluene only in solution) to the new complexes [Au2Ag2(C6X5)4L2]n [L = THF (2a, 2b), (CH3)2CO (3a, 3b), CH3CN (4a, 4b), C7H8 (5a, 5b)]. The crystal structures of 2a and 5a have been determined by X-ray diffraction methods, showing polymeric chains formed by the union of tetranuclear Au2Ag2 units via aurophilic interactions. The thermal stability and the vapochromic behaviour of these complexes have been studied by thermogravimetric analysis (TGA), X-ray powder diffraction and FT-IR spectroscopy
Luminescent Silver(I) and Copper(I) Systems Containing Pyridyl Phosphine Bridges
Authors: Crespo Olga , Gimeno M. Concepción , Laguna Antonio , Larraz Carmen
Published: February 2015

Luminescent silver(I) and copper(I) complexes containing pyridylphosphine ligands have been synthesized and structurally characterized by single crystal X-ray diffraction methods. The reaction of Ag(OTf) (OTf = trifluoromethanesulfonate) with 2-pyridyldiphenylphosphine in different molar ratios gives the species [Ag2(OTf)2(μ-PPh2py)2] (1), [Ag(PPh2py)2]OTf (2), [Ag(PPh2py)3]OTf (3), and [Ag2(PPh2py)3](OTf)2 (4) with several modes of coordination of the pyridylphosphine. The oxidation of the phosphine in compound 4 gave [Ag2(OTf)(μ-PPh2py)2(OPPh2py)]OTf (5) which has been structurally characterized. It shows two bridging phosphine ligands and one chelating OPPh2py ligand. The reactions of the silver salt with bis(2-pyridyl)phenylphosphine in different molar ratios affords the complex [Ag2(OTf)2(μ-PPhpy2)2] (6), while the corresponding reactions with [Cu(NCMe)4]PF6 lead to two different compounds, namely [Cu2(NCMe)2(μ-PPhpy2)2](PF6)2 (7) and [Cu2(PPhpy2)2(μ-PPhpy2)2](PF6)2 (8). All complexes exhibit luminescence in the solid state at room temperature and at 77 K