Eigenvalue approach to study the effect of rotation and relaxation time in generalized magneto-thermo-viscoelastic medium in one dimension

The fundamental equations of the problems of generalized thermoelasticity with one relaxation parameter including heat sources in infinite rotating magneto-thermo-viscoelastic media have been derived in the form of a vector matrix differential equation in the Laplace transform domain for a one dimensional problem. These equations have been solved by the eigenvalue approach to determine deformations, stress, and temperature. The results have been compared to those available in the existing literature. The graphs have been drawn to show the effect of rotation in the medium.     

Towards an enantiospecific total synthesis of garsubellin A and related phloroglucin natural products: the α-pinene approach

The first enantiospecific approach to garsubellin A and related phloroglucin natural product nemorosone, of contemporary interest from (−)-α-pinene, has been delineated. Through a series of stereospecific operations, the requisite stereochemistry of the prenyl groups has been secured. Kende cyclization has been employed as the key step to construct the functionalized bicyclo[3.3.1]nonane core.     

Silver-palladium nanodispersions in silicate matrices: highly uniform, stable, bimetallic structures

Ag-Pd nanobimetallic colloidal particles are prepared in a single step by a chemical reduction method. Organically modified aminosilicate is used as a supporting matrix as well as a stabilizing agent, to obtain very uniform, well-distributed bimetallic particles. These nanoparticles are found to be stable for several months in both the solid and the liquid phases. The structure of the bimetallic particles has been followed by X-ray photoelectron spectroscopy and ultraviolet-visible spectroscopy. The distribution and the particle size are determined by transmission electron microscope and X-ray diffraction studies. Polymerization and condensation of the support silicate material have been confirmed by Fourier transform infrared spectroscopy.     

A study of structural and bonding variations in the homologous series [Mo(2)(CN)(6)(dppm)(2)](n-) (n = 2, 1, 0)

Reaction of Mo(2)Cl(4)(dppm)(2) (dppm = bis(diphenylphosphino)methane) with 6 equiv of [n-Bu(4)N][CN] or [Et(4)N][CN] in dichloromethane yields [n-Bu(4)N](2)[Mo(2)(CN)(6)(dppm)(2)] (1) and [Et(4)N](2)[Mo(2)(CN)(6)(dppm)(2)] (2), respectively. The corresponding one- and two-electron oxidation products [n-Bu(4)N][Mo(2)(CN)(6)(dppm)(2)] (3) and Mo(2)(CN)(6)(dppm)(2) (4)were prepared by reactions of 1 with the oxidant NOBF(4). Single-crystal X-ray structures of 2.2CH(3)CN, 3.2CH(3)CN.2H(2)O, and 4.2CH(3)NO(2) were performed, and the results confirmed that all three complexes contain identical ligand sets with trans dppm ligands bisecting the Mo(2)(mu-CN)(2)(CN)(4) equatorial plane. The binding of the bridging cyanide ligands is affected by the oxidation state of the dimolybdenum core as evidenced by an increase in side-on pi-bonding overlap of the mu-CN in going from 1 to 4. The greater extent of pi-donation into Mo orbitals is accompanied by a lengthening of the Mo-Mo distance (2.736(1) A in Mo(2)(II,II) (2), 2.830(1) A in Mo(2)(II,III) (3), and 2.936(1) A in Mo(2)(III,III) (4)). A computational study of the closed-shell members of this homologous series, [Mo(2)(CN)(6)(dppm)(2)](n)() (n = 2-, 0), indicates that the more pronounced side-on pi-donation evident in the X-ray structure of 4 leads to significant destabilization of the delta orbital and marginal stabilization of the delta() orbitals with respect to nearly degenerate delta and delta orbitals in the parent compound, 2. The loss of delta contributions combined with the reduced orbital overlap due to higher charges on molybdenum centers in oxidized complexes 3 and 4 is responsible for the observed increase in the length of the Mo-Mo bond.     

Characterization and reactivity study of non-heme high-valent iron–hydroxo complexes

A terminal Fe^IIIOH complex, [Fe^III(L)(OH)]²⁻ (1), has been synthesized and structurally characterized (H₄L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of 1 with one equiv. of tris(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium nitrate (CAN) in acetonitrile at −45 °C results in the formation of a Fe^IIIOH ligand radical complex, [Fe^III(L˙)(OH)]⁻ (2), which is hereby characterized by UV-visible, ¹H nuclear magnetic resonance, electron paramagnetic resonance, and X-ray absorption spectroscopy techniques. The reaction of 2 with a triphenylcarbon radical further gives triphenylmethanol and mimics the so-called oxygen rebound step of Cpd II of cytochrome P450. Furthermore, the reaction of 2 was explored with different 4-substituted-2,6-di-tert-butylphenols. Based on kinetic analysis, a hydrogen atom transfer (HAT) mechanism has been established. A pK_a value of 19.3 and a BDFE value of 78.2 kcal/mol have been estimated for complex 2.

One-electron oxidation of an Fe^III–OH complex (1) results in the formation of a Fe^III–OH ligand radical complex (2). Its reaction with (C₆H₅)₃C˙ results in the formation of (C₆H₅)₃COH, which is a functional mimic of compound II of cytochrome P450.     

Cyclic perfluorocarbon radicals and anions having high global warming potentials (GWPs): structures, electron affinities, and vibrational frequencies

Adiabatic electron affinities, optimized molecular geometries, and IR-active vibrational frequencies have been predicted for small cyclic hydrocarbon radicals C(n)H(2)(n)(-)(1) (n = 3-6) and their perfluoro counterparts C(n)F(2)(n)(-)(1) (n = 3-6). Total energies and optimized geometries of the radicals and corresponding anions have been obtained using carefully calibrated (Chem. Rev. 2002, 102, 231) density functional methods, namely, the B3LYP, BLYP, and BP86 functionals in conjunction with the DZP++ basis set. The predicted electron affinities show that only the cyclopropyl radical tends to bind electrons among the hydrocarbon radicals studied. The trend for the perfluorocarbon (PFC) radicals is quite different. The electron affinities increase with expanding ring size until n = 5 and then slightly decrease at n = 6. Predicted electron affinities of the hydrocarbon radicals using the B3LYP hybrid functional are 0.24 eV (C(3)H(5)/C(3)H(5)(-)), -0.19 eV (C(4)H(7)/C(4)H(7)(-)), -0.15 eV (C(5)H(9)/C(5)H(9)(-)), and -0.11 eV (C(6)H(11)/C(6)H(11)(-)). Analogous electron affinities of the perflurocarbon radicals are 2.81 eV (C(3)F(5)/C(3)F(5)(-)), 3.18 eV (C(4)F(7)/C(4)F(7)(-)), 3.34 eV (C(5)F(9)/C(5)F(9)(-)), and 3.21 eV (C(6)F(11)/C(6)F(11)(-)).     

Kinetic Studies on Interaction of Platinum(II) Complexes with an ‘S’ Containing Ligand in Aqueous Medium

The kinetics of the substitution reactions of [Pt(dach)(H₂O)₂]²⁺ and [Pt(en)(H₂O)₂]²⁺ (where ‘dach’ and ‘en’ are cis-1,2-diaminocyclohexane and ethylenediamine, respectively) with excess N,N′-diethylthiourea have been studied in aqueous solution by UV–Vis spectrophotometry. The effect of different N–N spectator ligands on the reactivity of platinum(II) complexes was investigated by studying the water lability of the reactant complexes. The kinetic study has been substantiated by product isolation, IR, NMR and ESI-MS spectral analysis and DFT calculations. The reactions follow normal square-planar substitution mainly in an associative way. Rate parameters have been evaluated under different conditions. The substitution rates of the complexes studied can be tuned through the nature of the N–N chelates, which is important in the development of new active compounds for cancer therapy.     

Bulky,spherical, and fluorinated anion BAr induces ‘on-water’ activity of silver salt for the hydration of terminal alkynes

AgBAr^F displays remarkable ‘on-water’ activity for catalytic hydration of terminal alkynes although it is ineffective in common organic solvents. Liquid alkynes do not require additive or co-solvent whereas a small amount of ethyl acetate triggers quantitative conversions for solid alkynes.