Experimental and computational investigations of a cadmium(II) mononuclear complex with 2,6-Bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp) and selenocyanate as ligands

A new cadmium (II) complex, [Cd(bdmpp)(SeCN)₂(H₂O)] (1) (where bdmpp = 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine), has been synthesized and characterized by elemental and spectral (IR, ¹H-NMR and ¹³C-NMR, UV-Vis) analyses, differential scanning calorimetry, and single crystal X-ray diffraction studies. X-ray analysis showed that the structure was crystallized in the monoclinic space group Cc with a = 9.031(2), b = 13.884(3), c = 16.910(3) Å, and Z = 4. The geometry around the cadmium atom is distorted octahedral with a CdN₃Se₂O setup. The N atoms of the SeCN are engaged in two strong intermolecular H-bonding interactions forming a 3D supramolecular polymeric network. The geometry and vibrational frequencies of complex 1 computed with the DFT methods (BLYP, B3LYP, B3PW91, MPW1PW91) are in better agreement with experiment than those obtained with the ab-initio method except for the bond angles. The molecular orbital diagram has been also calculated and visualized at the B3LYP/LanL2DZ level of theory.      

Hexakis(4-phormylphenoxy)cyclotriphosphazene: X-ray and DFT-calculated structures

The crystal structure of hexakis(4-phormylphenoxy)cyclotriphosphazene is determined by using X-ray diffraction and then the molecular structure is investigated with density functional theory (DFT). X-Ray study shows that the title compound has C-H…π interaction with phosphazene ring. The molecules in the unit cell are packed with Van der Waals and dipole-dipole interactions and the molecules are packed in zigzag shaped. Optimized molecular geometry is calculated with DFT at B3LYP/6-311G(d,p) level. The results from both experimental and theoretical calculations are compared in this study.     

Non-Darcian Forced Convection Flow of Viscous Dissipating Fluid over a Flat Plate Embedded in a Porous Medium

In this study, laminar boundary layer flow over a flat plate embedded in a fluid-saturated porous medium in the presence of viscous dissipation, inertia effect and suction/injection is analyzed using the Keller box finite difference method. The flat plate is assumed to be held at constant temperature. The non-Darcian effects of convection, boundary and inertia are considered. Results for the local heat transfer parameter and the local skin friction parameter as well as the velocity and temperature profiles are presented for various values of the governing parameters. The non-Darcian effects are shown to decrease the velocity and to increase the temperature. It is also shown that the local heat transfer parameter and the local skin friction parameter increase due to suction of fluid while injection reverses this trend. It is disclosed that the effect of the viscous dissipation for negative values of Ec (T _w < T _∞) is to enhance the heat transfer coefficient while the opposite is true for positive values of Ec (T _w > T _∞). The results are compared with those available in the existing literature and an excellent agreement is obtained.     

trans‐Bis[1‐benzyl‐3‐(2,3,4,5,6‐penta­fluoro­benz­yl)benzimidazol‐2‐yl­idene]­dibromo­palladium(II)

The title compound, [PdBr₂(C₂₁H₁₃F₅N₂)₂], crystallizes with two independent centrosymmetric conformational isomers having a square‐planar coordination at the Pd atom. The conformational isomers differ by the ligands having a cis or trans orientation of their benzyl and pentafluorobenzyl rings with respect to the benzimidazole ring plane. The benzimidazole rings are rotated with respect to the coordination plane of the metal by 79.1 (2) and 75.2 (1)° for mol­ecules A and B, respectively. The Pd—Br bond lengths are 2.4218 (8) and 2.4407 (10) Å for mol­ecules A and B, respectively, and the Pd—C bond lengths are 2.030 (8) and 2.018 (9) Å. The crystal structure contains two types of C—H⋯F and one type of C—H⋯Br intra­molecular contact, as well as C—H⋯π inter­actions.     

Chirality transfer during alkylation of chiral amides

Chiral amides derived from O-methyl mandelic acid and achiral amines underwent enantioselective alpha-methylation on treatment with LTMP followed by addition of methyl iodide; chirality transfer from an undeprotonated chiral amide into an achiral enolate in a mixed aggregate is supposed to be responsible for the asymmetric induction.