Metal Complexes with Macrocyclic Ligands. XIV. Formation,dissociation and metal exchange with an N2S2-macrocycle

10, 10, 12-Trimethyl-3,4-benzo-1,6-dithia-9,13-diazacyclopentadecen-dihydrochloride (LH, 2 ) and its Ni²⁺ complex were synthesized and their reactivity studied. The formation kinetics of 2 with Cu²⁺ were found to be a second order reaction between Cu²⁺ or CuACO⁺ and the monoprotonated form of the ligand LH⁺. The rate constant k = 29 M ^?1S ^?1 is 10⁵–10⁶ times smaller than those of monoprotonated tetraazamacrocycles either because of second bond formation or because of a strong electrostatic interaction between the positive charges of the Cu²⁺ and the ammonium group. The metal-metal exchange between NiL⁺ and Cu²⁺ was also investigated. The reaction is independent of [Cu²⁺] and has the same rate and activation parameters as the dissociation of NiL²⁺. In contrast to open chain ligands, no mixed complex CuNiL⁴⁺ as intermediate was observed.     

Room Temperature Synthesis of Noble Metal Clusters in the Mesopores of Mechanically Strong Silica-Polymer Aerogel Composites

Clusters of Ag and Au have been formed in the bulk of mechanically strong silica-polymer aerogel composite monoliths. For that purpose, base-catalyzed silica hydrogels were washed with a 50% w/w acetone/diisocyanate (di-ISO) solution, and cured at 55°C for 3 days. Unreacted di-ISO solution was washed off with acetone, and the gels were washed with a acetone solutions of Ag⁺ or AuCl^– ₄ (3 × 10^–4 mol · L^–1), containing also 0.2 mol · L^–1 of 2-propanol as radical scavenger. Metal clusters were formed upon radiolytic reduction ( rays, 48–72 h, 7–7.5 kGy) of the precursor ions. After irradiation, the hydrogels were washed with acetone, and dried in supercritical CO₂. The resulting aerogel monoliths had a density of 0.56 g·cm^–3, a surface area of about 160 m² · g^–1, and an average pore diameter of about 200 nm. Transmission electron microscopy showed that the metal clusters are free of contamination, with a cubic face centered structure, and a narrow size distribution, centered around 10 nm. The elastic module, measured with a three-point flexural bending method, was in the 60–70 MPa range, and the load at rupture between 16 and 19 kg. Thermogravimetric analysis showed that the composites were stable up to about 300°C. These results are in excellent agreement with results obtained previously for as-grown, di-ISO cross-linked silica aerogels, and show that addition of metal clusters and gamma irradiation to a dose corresponding to a permanence of several years in low earth orbit at high inclination did not affect the chemical identity, the mechanical strength, the porosity and the bulk density of the composite aerogel monoliths.     

Tuning the redox chemistry of 4-benzoyl-N-methylpyridinium cations through para substitution. Hammett linear free energy relationships and the relative aptitude of the two-electron reduced forms for H-bonding

In anhydrous CH3CN a series of nine 4-(4-substituted-benzoyl)-N-methylpyridinium cations (substituent: -OCH3, -CH3, -H, -SCH3, -Br, -Ctbd1;CH, -CHO, -NO2, and -(+)S(CH3)2) demonstrate two chemically reversible, well-separated one-electron (1-e) reductions in the same potential range as other main stream redox catalysts such as quinones and viologens. Hammett linear free energy plots yield excellent correlation between the E(1/2) values of both waves and the substituent constants sigma(p)(-)(X). The reaction constants for the two 1-e reductions are rho(1) = 2.60 and rho(2) = 3.31. The lower rho(1) value is associated with neutralization of the pyridinium ring, and the higher rho(2) value with the negative charge developing during the 2nd-e reduction. Structure-function correlations point to a purely inductive role for substitution in both 1-e reductions. The case of the 4-(4-nitrobenzoyl)-N-methylpyridinium cation is particularly noteworthy, because the 4-nitrobenzoyl moiety undergoes reduction before the 2nd reduction of the 4-benzoyl-N-methylpyridinium system. Correlation of the third wave of this compound with the 2nd-e reduction of the others yields sigma(p)(-NO)2*- = -0.97 +/- 0.02, thus placing the -NO2-* group among the strongest electron donors. Solvent deuterium isotope effects and maps of the electrostatic potential (via PM3 calculations) as a function of substitution support that 2-e reduced forms develop H-bonding with proton donors (e.g., CH3OH) via the O-atom. The average number of CH3OH molecules entering the H-bonding association increases with e-donating substituents. H-bonding shifts the 2nd reduction wave closer to the first one. This has important practical implications, because it increases the equilibrium concentration of the 2-e reduced form from disproportionation of the 1-e reduced form.     

Synthesis and characterization of novel oxotechnetium (99Tc and 99mTc) and oxorhenium complexes from the 2,2'-bipyridine (NN)/thiol (S) mixed-ligand system

The synthesis and characterization of oxotechnetium and oxorhenium mixed-ligand complexes of the general formula MO[NN][S](3) (M = (99)Tc and Re), where NN represents the bidentate ligand 2,2'-bipyridine and S represents a monodentate thiophenol, is reported. The complexes were prepared by ligand exchange reactions using (99)Tc-gluconate and ReOCl(3)(PPh(3))(2) as precursors for the oxotechnetium and oxorhenium complexes, respectively. Compound 1 (M = (99)Tc, S = 4-methylthiophenol) crystallizes in the monoclinic space group P2(1)/a, a = 23.12(1) A, b = 14.349(6) A, c = 8.801(4) A, beta = 94.81(2) degrees, V = 2918(2) A(3), Z = 4. Compound 3 (M = Re, S = 4-methylthiophenol) crystallizes in the monoclinic space group P2(1)/a, a = 23.018(9) A, b = 14.421(5) A, c = 8.775(3) A, beta = 94.78(1) degrees, V = 2903(2) A(3), Z = 4. Compound 4 (M = Re, S = 4-methoxythiophenol) crystallizes in the orthorhombic space group Pbca, a = 16.32(1) A, b = 24.55(2) A, c = 16.94(1) A, V = 6788(9) A(3), Z = 8. In all cases, the coordination geometry around the metal is distorted octahedral with the equatorial plane being defined by the three sulfur atoms of the thiophenols and one nitrogen atom of 2,2'-bipyridine, while the apical positions are occupied by the second nitrogen atom of 2,2'-bipyridine and the oxygen of the M=O core. The complexes are stable, neutral, and lipophilic. Complete (1)H and (13)C NMR assignments are reported for all complexes. The analogous oxotechnetium complexes have been also synthesized at tracer level ((99m)Tc) by mixing the 2,2'-bipyridine and the corresponding thiol with Na(99m)TcO(4) generator eluate using NaBH(4) as reducing agent. Their structure was established by chromatographic comparison with authentic oxotechnetium and oxorhenium complexes using high performance liquid chromatography techniques.     

Synthesis and characterization of the physical, chemical and mechanical properties of isocyanate-crosslinked vanadia aerogels

A strong lightweight material (X-VOx) was formulated by nanocasting a conformal 4 nm thin layer of an isocyanate-derived polymer on the entangled worm-like skeletal framework of typical vanadia aerogels. The mechanical properties were characterized under both quasi-static loading conditions (dynamic mechanical analysis, compression and flexural bending testing) as well as high strain rate loading conditions using a split Hopkinson pressure bar (SHPB). The effects of mass density, moisture concentration and low temperature on the mechanical properties were determined and evaluated. Digital image correlation was used to measure the surface strains through analysis of images acquired by ultra-high speed photography, indicating nearly uniform compression at all stages of deformation during compression. The energy absorption of X-VOx was plotted as a function of the density, strain rate and temperature, and compared with that of plastic foams. X-VOx remains ductile even at ?180 °C, a characteristic not found in most materials. This unusual ductility is derived from interlocking and sintering-like fusion of nanoworms during compression. X-VOx emerges as an ideal material for force protection under impact.     

A combinatorial access to 1,5-benzodiazepine derivatives and their evaluation for aldose reductase inhibition

Aryldiazepinothiophenones 4 were prepared from the reaction of o-phenylenediamines with acetone in the presence of 2-mercaptocarboxylic acids along with thiazolobenzodiazepines 6, thiazolobenzimidazoles 7 and 1,5-benzodiazepines 5, which were obtained as by-products. The benzodiazepinothiophenones 4a-d and the benzodiazepines 5a-d were also isolated from the reaction of o-phenylenediamines 1a-c with phorone. Structural assignments of the new compounds as well as complete assignment of ¹H and ¹³C NMR signals were based on the analysis of their ¹H and ¹³C NMR (1D and 2D), IR, MS and elemental analysis data. Compounds 4 were evaluated for aldose reductase inhibition and also as antioxidants.