Synthesis, structures and reactivity of triosmium clusters containing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands

Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os₃(CO)₁₂] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me₃NO in moderate yields. Compounds [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os₃(CO)₉(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh₃; 6, L′ = P(OMe)₃; 7, L′ = ^tBuNC; 8, L′ = C₅H₅N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms.     

New nickel(II), copper(II), platinum(II) and palladium(II) complexes of a multidentate sulfur–nitrogen chelating agent

A new, potentially polydentate sulfur–nitrogen chelating agent, 2,6–bis(N-methyl-S-methyldithiocarbazato)pyridine (L) has been synthesized and characterized. With nickel(II) salts, the ligand yields complexes of empirical formula NiLX2·nH2O (X=Cl−, NCS− or NO3−; n=0 or 1) in which it behaves as a quadridentate NSSN chelating agent, coordinating to the nickel(II) ion via the two amino nitrogen atoms and the two sulfur atoms. Magnetic and spectral evidence support a distorted octahedral structure for these complexes. The ligand reacts with copper(II), platinum(II) and palladium(II) salts to yield homo-binuclear complexes of general formula [M2LX4]·nSol (M=CuII, PtII or PdII; X=Cl− or Br−; n=0.5, 1 or 2; Sol=H2O, MeOH or MeCOMe), in which each of the metal ions is in a square-planar environment. These complexes have been characterized by a variety of physicochemical techniques. This revised version was published online in June 2006 with corrections to the Cover Date.     

Biologically active metabolites from fungi, 19: new isocoumarins and highly substituted benzoic acids from the endophytic fungus, Scytalidium sp

Six known metabolites, two new isocoumarins 4 and 8, and one new highly substituted benzoic acid derivative 9 were isolated from the ethyl acetate culture extract of a fungal endophyte, Scytalidium sp. In addition, another new benzoic acid 10 with an unusual 1,2-dicarbonyl side chain was indirectly identified from its methylated derivatives 10a-10d.     

Convenient Preparation of a Cyclopropanation Reagent: α-Siloxymethyliron Complex

A convenient preparation of α-siloxymethyliron complex (7) was developed from commercially available s-trioxane and/or paraformaldehyde. For synthetic utility, iron methylidene complex (8) was generated in situ from the α-siloxymethyliron complex (7) and cyclopropanes (10) by treatment with alkenes.     

Comparative analysis of refrigerant performance between LPG and R134a under subtropical climate

Journal of Thermal Analysis and Calorimetry - In this investigation, a series of experiments were conducted to explore the effects of liquefied petroleum gas (LPG) mixture of 60% propane and 40%...     

Regioselective Synthesis of Natural 6‐Prenylpolyhydroxyisoflavone (Lupisoflavone) and Lupisoflavone Hydrate with Hypervalent Iodine Reagents

The Pd(0)‐catalyzed coupling reaction of 6‐iodotetraalkoxyisoflavone, which was obtained from the oxidative rearrangement of 3′‐iodotetraalkoxychalcones, with 2‐methyl‐3‐butyn‐2‐ol in heating condition affords 6‐alkynylisoflavone. Hydrogenation of 6‐iodotetraalkoxyisoflavone followed by acid‐catalyzed dehydration with p‐TsOH·H₂O gave lupisoflavone.     

Synthesis and characterisation of cobalt complex of sulfathiazole with acetic acid

The synthesis and characterization of the Co(II) complex of sulfathiazole is presented here. The compound was characterised by spectroscopic methods and crystal structure of the complex was determined as well. The complex crystallizes in the triclinic crystal form with the space group of $\overline{P_1}$. The asymmetric unit of the title compound contains one tetrachlorocobaltate anion, two sulfathiazolium cations and one acetic acid molecule in the crystal lattice. The Co(II) ion exhibits tetrahedral environment surrounded by four chloride ions. The two sulfathiazolium cations are linked by O–H···N hydrogen bonds.     

Synthesis of Substituted Tricyclo[5.3.1.04,9]undecan‐2,6‐dione from 4,4‐Disubstituted Cyclohexanone Enamines and Methacryloyl Chloride

Morpholine enamines 4‐acetyl‐4‐methyl‐1‐morpholinocyclohexene 4a, 4‐acetyl‐4‐phenyl‐1‐morpholinocyclohexene 4b, and 4‐acetyl‐4‐isopropenyl‐1‐morpholinocyclohexene 4c react with methacryloyl chloride to give 1,7‐dimethyl‐4(N‐morpholino) tricyclo[5.3.1.0^4,9]undecan‐2,6‐dione 9a , 1‐phenyl‐7‐methyl‐4(N‐morpholino) tricyclo[5.3.1.0^4,9]undecan‐2,6‐dione 9b , and 1‐ispropenyl‐7‐methyl‐4(N‐morpholino) tricyclo[5.3.1.0^4,9]undecan‐2,6‐dione 9c respectively, along with the corresponding substituted adamandane‐2,4‐diones.     

Plasmonic Pollen Grain Nanostructures: A Three-Dimensional Surface-Enhanced Raman Scattering (SERS)-Active Substrate

A new route has been developed to design plasmonic pollen grain-like nanostructures (PGNSs) as surface-enhanced Raman scattering (SERS)-active substrate. The nanostructures consisting of silver (Ag) and gold (Au) nanoparticles along with zinc oxide (ZnO) nanoclusters as spacers were found highly SERS-active. The morphology of PGNSs and those obtained in the intermediate stage along with each elemental evolution has been investigated by a high-resolution field emission scanning electron microscopy. The optical band gaps and crystal structure have been identified by UV-vis absorption and X-ray powder diffraction (XRD) measurements, respectively. For PGNSs specimen, three distinct absorption bands related to constituent elements Ag, Au, and ZnO were observed, whereas XRD peaks confirmed the existence of Ag, Au, and ZnO within the composition of PGNSs. SERS-activity of PGNSs was confirmed using Rhodamine 6G (R6G) as Raman-active dyes. Air-cooled solid-state laser kits of 532 nm were used as excitation sources in SERS measurements. SERS enhancement factor was estimated for PGNSs specimen and was found as high as 3.5×10⁶. Finite difference time domain analysis was carried out to correlate the electromagnetic (EM) near-field distributions with the experiment results achieved under this investigation. EM near-field distributions at different planes were extracted for s-, p- and 45° of incident polarizations. EM near-field distributions for such nanostructures as well as current density distributions under different circumstances were demonstrated and plausible scenarios were elucidated given SERS enhancements. Such generic fabrication route as well as correlated investigation is not only indispensable to realize the potential of SERS applications but also unveil the underneath plasmonic characteristics of complex SERS-active nanostructures.