Titanocene(III) chloride mediated radical induced asymmetric synthesis of α-methylene bis-γ-butyrolactone

Asymmetric synthesis of α-methylene bis-γ-butyrolactone has been synthesized using titanocene(III) chloride as a radical source. Titanocene(III) chloride (Cp₂TiCl) was prepared in situ from commercially available titanocene dichloride (Cp₂TiCl₂) and zinc dust in THF.     

Syntheses, crystal structures and magnetic properties of two dicopper(II) complexes and a zigzag 1-D Cu(II) complex of a bidentate pyridyl-pyrazole ligand

Two new dinuclear copper compounds, [Cu₂(pypz)₂(N₃)₂(NO₃)₂] (1) and [Cu₂(pypz)₂(OH)₂(NO₃)₂] (2), and one 1-D polymeric Cu(II) complex, [Cu(pypz)(dca)₃]_n (3) [‘pypz’ = (3,5dimethyl-1-(2′-pyridyl)pyrazole) and dca = (dicyanamide)], have been synthesized and characterized crystallographically and spectroscopically. Complex 1 is pseudo-octahedral, adjacent Cu atoms are connected by a pair of μ(1,1) azido groups and the structure is stabilized by π-π interactions between two pyridyl moieties from two different neighboring complex molecules. Complexes 2 and 3 are square pyramidal. The hydroxo bridged complex 2 is further stabilized through H-bonding. The 1-D polymeric chain of 3 is bridged by an end-to-end dicyanamide bridge and it propagates along the crystallographic b axis, whilst the polymer chains are stacked one upon another along the crystallographic c axis. Low temperature magnetic measurement shows that complexes 1 and 2 are ferromagnetic (J values are 30.81 and 14.79 cm⁻¹, respectively), whereas due to larger Cu-Cu distances, complex 3 shows weak ferromagnetism.     

Optically definable reaction-diffusion-driven pattern generation of Ag-Au nanoparticles on templated surfaces

We introduce a new lithographic method for the generation of 2D patterns of composite nanoparticles (NPs) of Ag and Au by taking recourse to combine top-down and bottom-up approaches. Micrometer-scale and submicrometer-scale patterned Ag foils of commercially available compact disks (CDs) and digital versatile disks (DVDs), respectively, were used as templates. The galvanic replacement reaction of Ag by HAuCl(4) in the presence of the dye coatings on the foils led to the formation of patterned NP composites of Ag and Au, in addition to the formation of AgCl. The resultant structures appeared in the form of cross patterns of particles with micrometer and submicrometer dimensions. The AgCl crystals thus formed could be removed by using either a saturated NaCl solution or aqueous ammonia. In addition, AgCl could be converted to Ag by electrochemical reduction, thus generating Ag-coated Au NPs. Interestingly, the digital writing on CDs led to the formation of tertiary imprints on the patterns, based on the original writing patterns. This provided an additional handle in generating hierarchical patterns using light in combination with a chemical reaction diffusion process and the nearly parallel line patterns originally present in commercial CDs. The reactions could be carried out in aqueous solution, and the method does not require any additional curing. Also, the density of patterned particles is scalable on the basis of the choice of the original line patterns as present in CDs and DVDs.     

Organogel-hydrogel transformation by simple removal or inclusion of N-Boc-protection

Development of organo- and hydrogelators is on the rise because of their extensive applications, from advanced materials to biomedicine. However, designing both types of gelator from a common structural scaffold is challenging, and becomes more significant if transformation between them can be achieved by a simple method. The present work reports the design and synthesis of both organo- and hydrogelators from amino acid/peptide-based amphiphilic precursors with a naphthyl group at the N terminus and a primary amine-containing hydrophilic ethyleneoxy unit at the C terminus. In alkaline medium, tert-butyloxycarbonyl (Boc) protection at the primary amine of the amphiphiles resulted in efficient organogelators (minimum-gelation concentration (MGC)=0.075-1.5% w/v). Interestingly, removal of the Boc protection from the ethyleneoxy unit, under acidic conditions, yielded amphiphiles capable of gelating water (MGC=0.9-3.0% w/v). Simple protection and deprotection chemistry was used to achieve transformation between the organogel and hydrogel by alteration of the pH. Combinations of different aliphatic and aromatic amino acids were investigated to discover their cumulative effect on the gelation properties. Field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) were employed to investigate the supramolecular morphology of the thermoreversible gels. Spectroscopic investigations (FTIR, photoluminescence, XRD) revealed that noncovalent interactions, such as hydrogen bonding, π-π stacking, and van der Waals interactions play a decisive role in self-assembled gelation.     

Total chemical synthesis of biologically active vascular endothelial growth factor

Efficient access: the 204-residue covalent-dimer vascular endothelial growth factor with full mitogenic activity was prepared from three unprotected peptide segments by one-pot native chemical ligations. The covalent structure of the synthetic VEGF was confirmed by precise mass measurement, and the three-dimensional structure of the synthetic protein was determined by high-resolution X-ray crystallography.     

The association reaction between C2H and 1-butyne: a computational chemical kinetics study

The potential energy surfaces (PES) for the reaction of the C(2)H radical with 1-butyne (C(4)H(6)) have been studied using the CBS-QB3 method. Density functional B3LYP/cc-pVTZ and M06-2X/6-311++G(d,p) calculations have also been performed to analyze the reaction energetics. For detailed theoretical calculation on the total reaction mechanism, the initial association reactions on more and less substituted C atoms of 1-butyne are treated separately followed by a variational transition state theory (VTST) calculation to obtain reaction rates. The successive unimolecular reactions from the association reaction complexes are subjected to Rice-Ramsperger-Kassel-Marcus (RRKM) calculations for reaction rate constants and product branching ratios. The calculated rate constants in the temperature range 70-295 K for both the association reactions are found to be highly temperature dependent at low temperatures, which is contrary to the experimental findings of temperature independent association rates. We have explained this observation with the help of variational nature of the transition states, and we found a "loose" transition state at low temperatures. The calculated product branching ratios for the unimolecular reactions generally agree with the available experimental data, although some channels show a significant method dependency and therefore the correlation with experiment is lost to some extent. Our detailed reaction energetics calculations confirm that the C(2)H + C(4)H(6) reaction proceeds without an entrance barrier and leads to the important products ethynylallene + CH(3), 1,3-hexadiyne + H, 3,4-hexadiene-1-yne + H, 2-ethynyl-1,3-butadiene + H, 3,4-dimethylenecyclobut-1-ene + H and fulvene + H exothermic by 25-75 kcal mol(-1), with strong dependence of the product distribution on the association mode of C(2)H with C(4)H(6), making these reactions fast under low temperature conditions of Titan's atmosphere. Therefore this study can provide a detailed picture of the complex hydrocarbon formation mechanism in the upper atmosphere.     

Kinetics and mechanism of the oxidation of hydroxylamine by a {Mn3O4}4+ core in aqueous acidic media

In this work we report the kinetics of oxidation of hydroxylamine by a trinuclear Mn(IV) oxidant, [Mn(3)(μ-O)(4)(phen)(4)(H(2)O)(2)](4+) (1, phen = 1,10-phenanthroline), in aqueous solution over a pH range 2.0-4.0. The trinuclear Mn(IV) species (1) deprotonates in aqueous solution at physiological pH: 1 ? 2 + H(+); pK(1) = 4.00 (± 0.15) at 25.0 °C, I = 1.0 (M) NaNO(3). Both 1 and 2 are reactive oxidants reacting with the conjugate acid of hydroxylamine, viz. NH(3)OH(+) where the deprotonated oxidant 2 reacts faster. This finding is in contrast to a common observation and belief that protonated oxidants react quicker than their deprotonated analogues. Mn(IV)(3) to Mn(II) transition in the present reaction proceeds through the intervention of a spectrally detected mixed-valent Mn(III)Mn(IV) dimer that quickly collapses to Mn(II). The rate of the reaction was found to be lowered in D(2)O-enriched media in comparison to that in pure H(2)O media. An initial one electron one proton transfer to Mn(IV)(3) (electroprotic; 1e, 1H(+)) could be mechanistically conceived as the rate step. We also demonstrate by means of high level DFT studies that, among the two sets of Mn(IV) atoms in the trinuclear oxidant, the unique one that is coordinated with two phen ligands and two oxo-bridges is reduced to Mn(III) at the rate step. This is explained based on energetic and spin density calculations. Moreover, this result agrees with the charge distribution on the Mn atoms of the trinuclear complex.     

Isolation of four new CoII/CoIII and NiII complexes with a pentadentate Schiff base ligand: syntheses, structural descriptions and magnetic studies

In this paper we report the temperature and pH dependent syntheses and systematic characterization of four new Co(II)/Co(III) and Ni(II) complexes with a pentadentate Schiff base ligand H(3)L obtained by condensing 1,3,-diaminopropan-2-ol with 2-hydroxyacetophenone in 1:2 molar ratio. The room temperature syntheses involving Co(II) and Ni(II) nitrates and the ligand H(3)L lead to the isolation of the dinuclear species [Co(2)L(2)(H(2)O)] (1), and the mononuclear complex [Ni(LH)] (3), respectively, whereas refluxing at basic pH leads to the tetranuclear complexes, [Co(II)(2)Co(III)(2)L(2)(μ(3)-OMe)(2)(NO(3))(H(2)O)(2)]NO(3)·2(H(2)O) (2), and [Ni(4)L(2)(μ(3)-OMe)(2)(H(2)O)(2)]·2H(2)O (4). 1 is found to be a simple mono alkoxo-bridged Co(III) dinuclear species, whereas 2 and 4 are both rhomb-like tetrameric complexes with double oxo bridges and μ(3)-methoxo bridges, derived from the methanol solvent, in an open dicubane arrangement. Moreover 2 shows six coordinate ordered Co(II) and Co(III) ions and 4 has both six- and five-coordinate Ni(II) centers. Compound 3 is assigned a tentative mononuclear structure based on IR, UV-Vis spectroscopic, (1)H-NMR and ESI mass study results and is supposed to have one Ni(II) center coordinated with a ligand fragment in square planar geometry. The variable temperature magnetic susceptibility study for 2 and 4 is performed which indicate for both 2 and 4 the presence of intracluster dominant ferromagnetic interactions.