Ansa‐Bridged Bis(benzene) Titanium Complexes

Taking advantage of an improved synthesis of [Ti(η⁶‐C₆H₆)₂], we report here the first examples of ansa‐bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η⁶‐C₆H₆)₂] with nBuLi in the presence of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1′‐dilithio salt [Ti(η⁶‐C₆H₅Li)₂] ? pmdta that enables the preparation of the first one‐ and two‐atom‐bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η⁶‐C₆H₆)₂] is found to react with the Lewis base 1,3‐dimethylimidazole‐2‐ylidene (IMe) to give the bent sandwich complex [Ti(η⁶‐C₆H₆)₂(IMe)].     

Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries

A novel route for the synthesis of poly(ethylene glycol)‐b‐polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one‐pot procedure under near‐visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1⁻¹ and a polydispersity index of 1.20.

     

Synthesis of Furo[2,3‐d]pyridazin‐4(5H)‐one and Its N(5)‐Substituted Derivatives

We report the efficient preparation of furo[2,3‐d]pyridazin‐4(5H)‐one and its N‐substituted derivatives starting from methyl 2‐methylfuran‐3‐carboxylate. The Me group was converted to the aldehyde group, which was then condensed with hydrazine derivatives. Then, the ester functionalities were hydrolyzed to the corresponding acids, followed by treatment with SOCl₂ to give N‐substituted furopyridazinone derivatives.     

Spectral measurements of inductively coupled and helicon discharge modes of a laboratory argon plasma source

An experimental study was conducted to investigate the effects of several operational parameters in the emission spectra, in the 400-850 nm wavelength region, of a laboratory Argon plasma source. In particular, the emission spectra of the inductively coupled plasma and the Helicon plasma modes of operation were compared. Comparisons of spectra point to a significant increase in the ionization fraction of the plasma for the Helicon mode of operation. The spectral measurements allow one to determine the major trends in the plasma electron density for various parameters such as power delivered to the helical antenna, propellant mass flow rate, and applied external magnetic field intensity.Analysis of a prominent Argon single ion line, at 434.8 nm, points out that the plasma electron density increases linearly with the power delivered to the helical antenna, and that there is an optimum propellant mass flow rate for maximum ionization fraction. Additional analysis of the same line shows that above a minimum applied axial magnetic field intensity, the variation in the magnetic field strength has little effect on the plasma electron density.     

Cationic gold carbonyl complex on a phosphine support

A cationic gold carbonyl complex has been synthesized and characterized using several techniques including X-ray crystallography. [(Mes(3)P)Au(CO)][SbF(6)] (Mes = 2,4,6-Me(3)C(6)H(2)) has a linear, two-coordinate gold atom. This compound displays the CO stretching frequency at 2185 cm(-1). The (13)C NMR signal of the gold-bound (13)CO appears as a doublet centered at δ 182.6 ((2)J(C,P) = 115 Hz). A computational study shows that the Au-CO bond consists of electrostatic attraction, Au ← CO donation, and significant Au → CO π-back-bonding components. Polarization of the CO bond caused by the electrostatic effect of the cationic gold center is mainly responsible for the large blue shift in the CO stretching frequency.     

Quantum chemical computational studies on 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester

The optimized molecular geometry, vibrational frequencies, and gauge including atomic orbital (GIAO) (1)H and (13)C NMR shift values of 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester have been calculated by using Hartree-Fock (HF) and density functional method (DFT/B3LYP) with 6-31G(d), 6-31G(d,p) and LANL2DZ basis sets. The optimized molecular geometric parameters were presented and compared with the data obtained from X-ray diffraction. In order to fit the calculated harmonic wavenumbers to the experimentally observed ones, scaled quantum mechanics force field (SQM FF) methodology was proceeded. Correlation factors between the experimental and calculated (1)H chemical shift values of the title compound in vacuum and in CHCl(3) solution by using the conductor-like screening continuum solvation model (COSMO) were reported. The calculated results showed that the optimized geometry well reproduces the crystal structure. The theoretical vibrational frequencies and chemical shifts are in very good agreement with the experimental data. In solvent media the energetic behavior of the title compound was also examined by using the B3LYP method with the 6-31G(d) basis set, applying the COSMO model. The obtained results indicated that the total energy of the title compound decreases with increasing polarity of the solvent. Furthermore, molecular electrostatic potential (MEP), natural bond orbital (NBO) and frontier molecular orbitals (FMOs) of the title compound were performed by the B3LYP/LANL2DZ method, and also thermodynamic parameters for the title compound were calculated at all the HF and B3LYP levels.     

Effects of the surface roughness on heat transfer of perpendicularly impinging co-axial jet

Current work presents the comparison of the cooling characteristics of roughened and smooth heated surfaces subjected to co-axial impinging jet. The work fluid is air and the data runs are performed for jet Reynolds numbers for 10,000, 20,000 and 40,000, and non-dimensional surface to jet exit spacing, H/D, from 1 to 10. The co-axial jet configuration is based on a fully developed pipe flow encountering a double-pipe arrangement and splitting between the two pipes. The inner to outer diameter ratio is 0.5. A straight pipe without inner section is used as the circular jet. The impingement of circular jets to the roughened and smooth surfaces is also performed for comparison. Average Nusslet numbers were obtained to show the heat transfer enhancement from the surface. A good agreement between the literature and present paper was obtained. As a result, average Nusselt number with co-axial jet impingement to the roughened surface increased by up to 27% comparing to the circular jet impingement. In addition, the average Nusselt number increased with roughened surface by up to 6% over the whole surface area, comparing to the smooth surface.     

On the number of eigenvalues for parameter‐dependent diffusion problem on time scales

In this study, we consider parameter‐dependent diffusion eigenvalue problem on time scales. An upper bound on the number of eigenvalues for this problem on a finite time scale is given.