Metallo-organic domino reactions: C-H versus C-C bond breaking

HL and MeL are prepared by condensing benzil dihydrazone with 2-formylpyridine and 2-acetylpyridine, respectively, in 1:2 molar proportions. While in a reaction with [Ru(C(6)H(6))Cl(2)]2, HL yields the cation [Ru(C(6)H(6)){5,6-diphenyl-3-(pyridin-2-yl)-1,2,4-triazine}Cl]+, MeL gives the cation [Ru(C(6)H(6))(MeL)Cl]+. Both the cations are isolated as their hexafluorophosphate salts and characterised by X-ray crystallography. In the case of HL, double domino electrocyclic/elimination reactions are found to occur. The electrocyclic reaction occurs in a C=N-N=C-C=N fragment of HL and the elimination reaction involves breaking of a C-H bond of HL. Density functional calculations on model complexes indicate that the identified electrocyclic reaction is thermochemically as well as kinetically feasible for both HL and MeL in the gas phase. For a double domino reaction, similar to that operative in HL, to occur for MeL, breaking of a C-C bond would be required in the elimination step. Our model calculations show the energy barrier for this elimination step to be much higher (329.1 kJ mol(-1)) for MeL than that for HL (96.3 kJ mol(-1)). Thus, the domino reaction takes place for HL and not for MeL. This accounts for the observed stability of [Ru(C(6)H(6))(MeL)Cl]+ under the reaction conditions employed.     

Silver (I)-promoted asymmetric halohydrin reaction of chiral N-enoyl-2-oxazolidinones: scope and limitations

The halohydrin reaction of chiral N-enoyl-2-oxazolidinones 1 by halogen (Br₂/I₂) and water were efficiently carried out in aqueous organic solvent promoted by silver(I) with high anti- and regioselectivity and moderate to good diastereoselectivities. The alkenoyl, cinnamoyl and electron-deficient cinnamoyl substrates smoothly underwent bromohydrin reaction in aqueous acetone but no iodohydrin reaction, where as electron-rich cinnamoyl substrates preferred to undergo iodohydrin reaction in aqueous acetone with moderate diastereoselectivity and enhanced diastereoselectivity was observed in aqueous THF.     

o-hydroxylmethylphenylchalcogens: synthesis, intramolecular nonbonded chalcogen...OH interactions, and glutathione peroxidase-like activity

[Structure: see text]. The synthesis and characterization of a series of organochalcogen (Se, Te) compounds derived from benzyl alcohol 13 are described. The synthesis of the key precursor dichalcogenides 15, 22, and 29 was achieved by the ortho-lithiation route. Selenide 18 was obtained by the reaction of the dilithiated derivative 14 with Se(dtc)2. Oxidation of 15 and 22 with H2O2 afforded the corresponding cyclic ester derivatives 17 and 24, respectively. Oxidation of selenide 18 with H2O2 affords the spirocyclic compound 19. The presence of intramolecular interactions in dichalcogenides 15 and 22 has been proven by single-crystal X-ray studies. The cyclic compounds 17 and 19 have also been characterized by single-crystal X-ray studies. GP(X)-like antioxidant activity of selenium compounds has been evaluated by the coupled bioassay method. Density functional theory calculations at the mPW1PW91 level on ditelluride 22 have identified a fairly strong nonbonding interaction between the hydroxy oxygen and tellurium atom. The second-order perturbation energy obtained through NBO analysis conveys the involvement of n(O) --> sigma(Te-Te) orbital overlap in nonbonding interaction. Post wave function analysis with the Atoms in Molecules (AIM) method identified distinct bond critical point in 15 and 22 and also indicated that the nonbonding interaction is predominantly covalent. Comparison between diselenide 15 and ditelluride 22 using the extent of orbital interaction as well as the value of electron density at the bond critical points unequivocally established that a ditelluride could be a better acceptor in nonbonding interaction, when the hydroxy group acts as the donor.     

Charged spherically symmetric solution in Mikhail-Wanas field theory

A set of coupled differential equations obtained by Wanas in the Mikhail-Wanas generalized field theory is completely integrated.     

Two highly unsymmetrical tetradentate (N3O) Schiff base copper(II) complexes: Template synthesis,structural characterization,magnetic and computational studies

Two new copper(II) complexes, [Cu₂(L¹)₂](ClO₄)₂ (1) and [Cu(L²)(ClO₄)] (2), of the highly unsymmetrical tetradentate (N₃O) Schiff base ligands HL¹ and HL² (where HL¹ = N-(2-hydroxyacetophenone)-bis-3-aminopropylamine and HL² = N-(salicyldehydine)-bis-3-aminopropylamine) have been synthesised using a template method. Their single crystal X-ray structures show that in complex 1 two independent copper(II) centers are doubly bridged through phenoxo-O atoms (O1A and O1B) of the two ligands and each copper atom is five-coordinated with a distorted square pyramidal geometry. The asymmetric unit of complex 2 consists of two crystallographically independent N-(salicylidene)-bis(aminopropyl)amine-copper(II) molecules, A and B, with similar square pyramidal geometries. Cryomagnetic susceptibility measurements (5–300 K) on complex 1 reveal a distinct antiferromagnetic interaction with J = ?23.6 cm^?1, which is substantiated by a DFT calculation (J = ?27.6 cm^?1) using the B3LYP functional. Complex 1, immobilized over highly ordered hexagonal mesoporous silica, shows moderate catalytic activity for the epoxidation of cyclohexene and styrene in the presence of TBHP as an oxidant.     

Cascade synthesis of selective dihydro pyridazino fused acridinone derivatives via MCM-41 catalyzed ring-opening/ring-closure reaction

An enhanced one-pot synthesis of new functionalized 5,6-dihydro-5,5-dimethyl-2-phenyl-2H-pyridazino[3,4,5-kl]acridin-1(4H)-one derivatives with different substituted patterns by using mesoporous MCM-41 catalyst via a ring opening/ring closure reaction process has been established. This MCM-41 silica catalyst has been synthesized and characterized using an array of sophisticated analytical techniques like BET, XRD, UHRTEM, etc. This reaction could be conducted from inexpensive substrates within short period under neat reflux conditions. Compared with the usual methods, the remarkable advantages of this method are milder reaction conditions, operational simplicity, higher yields, short reaction times and an environmentally friendly procedure.     

N–H···π Interactions in Two Isomers of an Amino Group Containing <Emphasis Type="Italic">bis</Emphasis>-Phenol

Abstract  

Crystal structures of two bis-phenols namely bis-(3,5-dimethyl-2-hydroxyphenyl)(3-amino phenyl)methane 1 and bis-(3,5-dimethyl-4-hydroxyphenyl)(3-aminophenyl) methane 2 are determined. The compound 1 crystallises in monoclinic P2₁/c with a = 12.2579(16) ?, b = 16.0906(19) ?, c = 10.6664(13) ?, β = 115.417(7)°, V = 1900.2(4) ?³ whereas 2 crystallizes in monoclinic C2/c, a = 9.2538(2) ?, b = 18.6579(4) ?, c = 23.2725(5) ?, β = 98.796(2)°, V = 3970.89(15) ?³. The crystal lattice of both the compounds shows presence of N–H···π interactions but no O–H···π interactions.     

In situ electron beam irradiated rapid growth of bismuth nanoparticles in bismuth-based glass dielectrics at room temperature

In this study, in situ control growth of bismuth nanoparticles (Bi⁰ NPs) was demonstrated in bismuth-based glass dielectrics under an electron beam (EB) irradiation at room temperature. The effects of EB irradiation were investigated in situ using transmission electron microscopy (TEM), selected-area electron diffraction and high-resolution transmission electron microscopy. The EB irradiation for 2–8 min enhanced the construction of bismuth nanoparticles with a rhombohedral structure and diameter of 4–9 nm. The average particle size was found to increase with the irradiation time. Bismuth metal has a melting point of 271 °C and this low melting temperature makes easy the progress of energy induced structural changes during in situ TEM observations. This is a very useful technique in nano-patterning for integrated optics and other applications.     

Amplitude-frequency characteristics of non-linear vibrations of clamped elliptic plates carrying a concentrated mass

The influence of a concentrated mass on the amplitude-frequency characteristics of large amplitude-transverse vibrations of an isotropic clamped elliptic plate has been investigated by the application of the von Karman equations.     

Forced convection heat transfer from an equilateral triangular cylinder at low Reynolds numbers

An unsteady two-dimensional numerical simulation is performed to investigate the forced convection heat transfer for flow past a long heated equilateral triangular cylinder in an unconfined medium for the low Reynolds number laminar regime. The Reynolds number considered in this study ranges from 50 to 250 with three different values of Prandtl number (Pr?=?0.71, 7 and 100). Fictitious confining boundaries are chosen on the lateral sides of the computational domain that makes the blockage ratio β?=?5?% in order to make the problem computationally feasible. An unstructured triangular mesh is used for the computational domain discretization and the simulation is carried out with the commercial CFD solver Fluent. The flow and heat transfer characteristics are analyzed with the streamline and isotherm patterns at various Reynolds numbers. The dimensionless frequency of vortex shedding (Strouhal number), drag coefficient and Nusselt numbers are presented and discussed. The results obtained are in good agreement with the available results in the literature.