Eight novel Pt(II), Pd(II), Cu(II) and Zn(II) complexes with 4’-substituted terpyridine were synthesized and characterized by elemental analysis, UV, IR, NMR, electron paramagnetic resonance, high-resolution mass spectrometry and molar conductivity measurements. The cytotoxicity of these complexes against HL-60, BGC-823, KB and Bel-7402 cell lines was evaluated by MTT assay. All the complexes displayed cytotoxicity with low IC₅₀ values (<20 μm) and showed selectivity. Complexes , , and exerted 9-, 5-, 12- and 7-fold higher cytotoxicity than cisplatin against Bel-7402 cell line. The cytotoxicity of complexes , , , and was higher than that of cisplatin against BGC-823 cell line. Complexes , and showed similar cytotoxicity to cisplatin against KB cell line. Complex exhibited higher cytotoxicity than cisplatin against HL-60 cell line. Among these complexes, complex demonstrated the highest in vitro cytotoxicity, with IC₅₀ values of 1.62, 3.59, 2.28 and 0.63 μm against HL-60, BGC-823, Bel-7402 and KB cells lines, respectively. The results suggest that the cytotoxicity of these complexes is related to the nature of the terminal group of the ligand, the metal center and the leaving groups. Copyright © 2013 John Wiley & Sons, Ltd.

A straightforward, protecting-group-free protocol for the synthesis of chiral 6-substituted and 6,6’-disubstituted binols (binol = 1,1’-bi-2-naphthol) by palladium-catalyzed hydroxylation, C–N and C–O coupling of chiral 6-bromo- and 6,6’ -dibromo-1,1’-binaphthols is developed. The protecting group free palladium-catalyzed hydroxylation, C–O and C–N cross-coupling protocol affords a straightforward and general method for the synthesis of chiral 6-substituted and 6,6’-disubstituted binols with good yields, avoiding the tedious procedures of introduction and removal of protecting groups. Copyright © 2013 John Wiley & Sons, Ltd.

The steric effect of an aryloxido group on the synthesis and molecular structures of ytterbium aryloxides supported by β-diketiminato ligand L (L = [N(2,6-Me₂C₆H₃)C(Me)]₂CH⁻) is reported. Reactions of β-diketiminatoytterbium dichloride, LYbCl₂(THF)₂, with NaOAr¹ in THF (Ar¹ = [2,6-^tBu₂-4-MeC₆H₂], THF = tetrahydrofuran) at 60°C gave the corresponding ytterbium complexes LYb(OAr¹)Cl(THF) () and LYb(OAr¹)₂ (1), depending on the molar ratio of dichloride to sodium aryloxide, respectively, while the same reactions with NaOAr² and NaOAr³ (Ar² = [2,6-ⁱPr₂C₆H₃], Ar³ = [2,6-Me₂C₆H₃]) in 1:1 or 1:2 molar ratio in THF afforded only bisaryloxide complexes LYb(OAr²)₂(THF) (1) and LYb(OAr³)₂(THF) () in good yields, respectively. Complexes were fully characterized, including X-ray crystal structure analyses. All the complexes are efficient pre-catalysts for the catalytic addition of amines to carbodiimides giving guanidines. Copyright © 2013 John Wiley & Sons, Ltd.

A series of N-(ferrocenylmethyl amino acid) fluorinated benzene-carboxamide derivatives and have been synthesized by coupling ferrocenylmethyl amine 3 with various substituted N-(fluorobenzoyl) amino acid derivatives using the standard N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole protocol. The amino acids employed in this study were glycine and L-alanine. All of the compounds were fully characterized using a combination of ¹H NMR, ¹³C NMR, ¹⁹F NMR, distortionless enhancement by polarization transfer (DEPT)-135, ¹H–¹H correlation spectroscopy (COSY) and ¹H–¹³C COSY (heteronuclear multiple-quantum correlation) spectroscopy. The compounds were biologically evaluated on the oestrogen-positive MCF-7 breast cancer cell line. Compounds , , and exhibited cytotoxic effects on the MCF-7 breast cancer cell line. N-(Ferrocenylmethyl-L-alanine)-3,4,5-trifluorobenzene-carboxamide () was the most active compound, with an IC₅₀ value of 2.84 μm. Compounds , and had lower IC₅₀ values than that found for the clinically employed anticancer drug cisplatin (IC₅₀ = 16.3 μm against MCF-7). Guanine oxidation studies confirmed that was capable of generating oxidative damage via a reactive oxygen species-mediated mechanism. Copyright © 2013 John Wiley & Sons, Ltd.

A series of bis(phenoxy-imine) zirconium complexes bearing bulky o-bis(aryl)methyl-substituted aryl groups on the aniline moiety have been synthesized, characterized and tested as catalyst precursors for ethylene polymerization. ¹H NMR spectroscopy suggests that these complexes exist as a single chiral C₂-symmetric isomer in the solution. X-ray crystallographic analysis of the resulting biszwitterionic-type adduct complex C1 · 2HCl reveals that the phenoxy-imine groups function as a monodentate phenoxy ligand and the oxygen atoms are oriented trans to each other at the central metal atom. Using modified methylaluminoxane (MMAO) as co-catalyst, C1 · 2HCl, C2–C6 exclusively produce linear aluminium-terminated polyethylenes (Al-PEs) with high activity (up to 16.89 × 10⁶ g PE (mol Zr h)⁻¹, suggesting that chain transfer to aluminum is the predominant termination mechanism. It is noteworthy that the introduction of an excessively bulky o-bis(aryl)methyl substituent adjacent to the imine-N produces low molecular-weight Al-PEs (M_v 1.6–10.1 × 10³) due to the enhanced rate of chain transfer to alkylaluminium groups during polymerization. Copyright © 2013 John Wiley & Sons, Ltd.

Hydrogen silsesquioxane (HSQ) is an attractive electron-beam (e-beam) resist for sub-20 nm lithography owing to its high resolution, excellent line-edge roughness (LER) and good plasma etch resistance. However, the sensitivity and long-term stability of HSQ need to be significantly improved to have HSQ resists adopted for volume manufacturing. Here we develop novel organosilicate e-beam resists with improved e-beam sensitivity and stability as an alternative to HSQ resists. Copolymers of norbornene ethyltrimethoxysilane (NETMS) with 1,2-bis(triethoxysilyl)ethane, synthesized via acid-catalyzed sol–gel reactions, show excellent e-beam sensitivity with around a sixfold reduction in the critical dose as compared with HSQ but poor LER characteristics. Terpolymers were then synthesized using p-chloromethylphenyl trimethoxysilane (p-CMPTMS), NETMS and tetraethoxysilane, which exhibit significant improvement in sensitivity as compared with previously reported materials, together with high-resolution patterns and long-term stability. High-resolution patterns of features as small as 20 nm with excellent LER were successfully fabricated employing organosilicate terpolymers using a 100 keV e-beam. The dose for patterning 20 nm lines was reduced from 4000 μC cm⁻² for HSQ to 900 μC cm⁻² for an optimized terpolymer resist. FT-IR measurements suggest that the main reason for the increased e-beam sensitivity is chain transfer reaction between the norbornene moieties, which provide an efficient cross-linking mechanism by the e-beam generated radicals. Copyright © 2013 John Wiley & Sons, Ltd.

A series of ordered mesoporous organic–inorganic hybrid material was designed by using the amine-functionalized SBA-15 (PdX₂@SBA-15/N_Y, Y = 1, 2) as solid support for palladium complexes. Among them, the Pd(OAc)₂/ethylenediamine complex encapsulated into SBA-15 (Pd(OAc)₂@SBA-15/PrEn or Pd(OAc)₂@SBA-15/PrNHEtNH₂) exhibits higher activity and selectivity toward Suzuki cross-coupling reaction under aerobic conditions and water solvent mixture. The SBA-15/PrEn supported palladium pre-catalyst could be separated easily from reaction products and used repetitively several times, showing its superiority over homogeneous catalysts for industrial and chemical applications. Copyright © 2013 John Wiley & Sons, Ltd.

Mesoporous molecular sieve SBA-15 and conventional silica gel were grafted with 3-[2-(diethylamino)ethylamino]propyl groups and used as supports for the preparation of deposited palladium catalysts, which were subsequently evaluated in Stille cross-coupling reaction of aryl bromides. The highest conversions were achieved with the metal-saturated catalyst resulting from the modified SBA-15. Influence of various reaction parameters (solvent, additive, temperature, etc.) on the overall yield and selectivity was studied. Copyright © 2013 John Wiley & Sons, Ltd.

A series of new α-diimine nickel(II) catalysts bearing bulky chiral sec-phenethyl groups have been synthesized and characterized. The molecular structure of representative chiral ligand, bis[N,N′-(4-methyl-2,6-di-sec-phenethylphenyl)imino]-1,2-dimethylethane rac-1c and chiral complexes, {bis[N,N′-(4-methyl-2-sec-phenethylphenyl)imino]-2,3-butadiene}dibromidonickel rac-2a and bis{bis[N,N′-(4-methyl-2-sec-phenethylphenyl)imino]-2,3-butadiene}dibromidonickel rac-2b, were confirmed by X-ray crystallographic analysis. Complex rac-2c bearing two chiral sec-phenethyl groups in the ortho-aryl position and a methyl group in the para-aryl position, activated by diethylaluminum chloride (DEAC), showed highly catalytic activity for the polymerization of ethylene [4.12 × 10⁶ g PE (mol Ni.h.bar)⁻¹], and produced highly branched polyethylenes under low ethylene pressure (branching degree: 104, 118 and 126 branches/1000 C at 20, 40 and 60°C, respectively). Chiral 20-electron bis-α-diimine Ni(II) complex rac-2b also exhibited high activity toward ethylene polymerization [1.71 × 10⁶ g PE (mol Ni · h · bar)⁻¹]. The type and amount of branches of the polyethylenes obtained were determined by ¹H and ¹³C NMR. Copyright © 2013 John Wiley & Sons, Ltd.

Two new acylhydrazone copper(II) complexes of 4-hydroxy-N′-[(1E)-1-(4-methylphenyl)ethylidene]benzohydrazide (HL¹) and 4 ethyl [4-({(2E)-2-[1-(4-methylphenyl)ethylidene]hydrazinyl}carbonyl)phenoxy]acetate (HL²) have been synthesized and characterized. The structures of both acylhydrazone and copper(II) complexes were identified by elemental analysis, infrared spectra, UV–visible electronic absorption spectra, magnetic susceptibility measurements, TGA and powder X-ray diffraction. DNA binding and DNA cleavage activities of the synthesized copper complexes were examined by using UV-visible titration and agarose gel electrophoresis, respectively. The effect of complex concentration on the DNA cleavage reactions in the absence and presence of H₂O₂ was also investigated. The results indicate that all the complexes bind slightly to calf thymus DNA and cleavage pBR322 DNA. The mechanistic studies demonstrate that a hydrogen peroxide-derived species and singlet oxygen (¹O₂) are the active oxidative species for DNA cleavage. Copyright © 2013 John Wiley & Sons, Ltd.

Microwave chemistry is a green chemical method that improves reaction conditions and product yields while reducing solvent amounts and reaction times. This paper deals with the synthesis, spectral and biological studies of germanium(IV) complexes with chelating hydrazones derived from 1-(pyridine-2-yl)ethanone (F₁) and 1-(furan-2-yl)ethanone (F₂) with isonicotinohydrazide (INH). The complexes have been synthesized under a microwave–green chemical approach and investigated using a combination of microanalytical analysis, melting point, IR spectra, ¹H NMR spectra and ¹³C NMR spectra. Trimethylgermanium(IV)chloride and triphenylgermanium(IV)chloride interact with the hydrazones in a 1:1 molar ratio (metal:ligand), resulting in the formation of coloured products. On the basis of conductance and spectral evidence, a pentacoordinated structure for germanium(IV) complexes has been assigned for these products. The ligand is coordinated to the germanium(IV) via the azomethine nitrogen atom and the enolic oxygen atom. The free ligands and their metal complexes have been tested in male rats in order to assess their antifertility properties. Ligands and their metal complexes have also been tested in vitro against a number of pathogenic microorganisms in order to assess their antimicrobial and pesticidal properties. Both the ligands and their complexes were found to possess appreciable antifertility activity and other activities, which have been discussed in brief. Copyright © 2013 John Wiley & Sons, Ltd.

β-Bromo-α,β-unsaturated carboxylic acids are coupled and cyclized with terminal alkynes in DMF at 110°C in the presence of a catalytic amount of CuI and amino acid along with a base to give alkylidenefuranones in good yields. Similar reaction under microwave irradiation also gave alkylidenefuranones in higher yields. Copyright © 2013 John Wiley & Sons, Ltd.

Novel chiral thiolated amino alcohols were synthesized from norephedrine and thiophene carbaldehydes (methyl- or ethyl-substituted) and applied to the catalytic asymmetric Henry reaction of various aldehydes with nitromethane to provide β-hydroxy nitroalkanols in high conversion (92%). The reaction was optimized in terms of the metal, solvent, temperature and amount of chiral ligand. The corresponding catalyst with Cu(OTf)₂ and 2-propanol as the solvent provided the best enantioselectivities (up to 96% ee) of the corresponding nitroalcohols for aliphatic aldehydes. Copyright © 2013 John Wiley & Sons, Ltd.

We report the synthesis of mesoporous SBA-15 type silica bearing ionic imidazolium substructures. Surface functionalization was achieved via post-synthesis grafting reactions using bis-silylated imidazolium precursors onto a mesoporous SBA-15 type silica support. The grafting reactions were monitored via solid-state NMR spectroscopy, nitrogen sorption, transmission electron microscopy and thermogravimetry. Post-synthesis grafting is the most convenient way to achieve highly stable functionalized solids displaying excellent accessibility of the immobilized functional groups combined with high chemical stability. The solids obtained via post-synthesis grafting reactions appeared as highly efficient and reusable heterogeneous organocatalysts for Henry reactions and the cycloadditions of CO₂ to epichlorohydrin. Copyright © 2013 John Wiley & Sons, Ltd.

The immobilization of copper complexes by covalent anchoring of the ligand on the surface of mesoporous MCM-41 has been described. Bis[2-(phenylthio)benzylidene]-1,2-ethylenediamine as a new N₂S₂ donor salen-type ligand was covalently anchored onto nanopores of MCM-41 coordinated with copper (I) halide. The organic–inorganic hybrid material was achieved readily using 3-mercaptopropyltrimethoxysilane as a reactive surface modifier. 2-Nitrobenzaldehyde was reacted smoothly with the thiol moieties in order to form functionalized nanoporous silica with carbaldehyde groups. The resulting supported organic moieties were converted to thiosalen ligand and coordinated with CuX (X = CN, Cl, Br, I). Characterization of the heterogeneous catalyst by X-ray diffraction, N₂ sorption, FT-IR, diffuse reflectance UV-visible and TGA techniques indicated successful grafting of the copper complex inside the nano-channels of MCM-41. The heterogenized catalyst was evaluated by the Mannich condensation reaction of aldehydes, amines and alkynes. In this reaction, the corresponding propargylamines were obtained as single products in good to excellent yields. Factors such as reaction temperature, solvent, catalyst loading, leaching and reusability of the catalyst also were discussed. The use of MCM-41 as support permits an easier separation and recycles with only a marginal decrease in reactivity. Copyright © 2013 John Wiley & Sons, Ltd.

A series of half-sandwich ruthenium(II) arene complexes [(η⁶-p-cymene)Ru^II(R-BzTSC)Cl]Cl (BzTSC = benzaldehyde thiosemicarbazone and R = H, CH₃ and C₆H₅) have been synthesized and characterized by IR, ¹H NMR, UV-visible, electrospray ionization mass spectrometry and elemental analysis. The single-crystal structures of and have been determined. The molecular orbitals and electronic absorption spectra of the compounds have been calculated using the DFT and TDDFT methods. The in vitro antiproliferative activities of these complexes have been evaluated against four human cancer cell lines (CNE, H292, SKBR3 and Hey1-B), and is proved to be the most efficient inhibitor, with IC₅₀ values of 20, 31, 10 and 34 μm, respectively. Copyright © 2013 John Wiley & Sons, Ltd.

Novel diphosphinite ligands are synthesized by the reaction of various derivatives of 1,3-diols with chlorodiphenylphosphine. The synthesized ligands exhibited considerable impact on hydroformylation of various olefins with excellent regioselectivity toward branched aldehyde. The effect of solvent, temperature, pressure and catalyst loading on the hydroformylation reaction is also described. The synthesized diphosphinite ligands with rhodium precursor works under milder reaction conditions as compared to traditional phosphine and phosphite-based ligands. Copyright © 2013 John Wiley & Sons, Ltd.