Comparison of Iridium(I) Catalysts in Temperature Mediated Hydrogen Isotope Exchange Reactions

The reactivity and selectivity of iridium(I) catalysed hydrogen isotope exchange (HIE) reactions can be varied by using wide range of reaction temperatures. Herein, we have done a detailed comparison study with common iridium(I) catalysts ( 1 – 6 ) which will help us to understand and optimize the approaches of either high selectivity or maximum deuterium incorporation. We have demonstrated that the temperature window for these studied iridium(I) catalysts is surprisingly very broad. This principle was further proven in some HIE reactions on complex drug molecules.     

On vector variational-like inequalities and vector optimization problems with (G,α)-invexity

The aim of this paper is to study the relationship among Minty vector variationallike inequality problem, Stampacchia vector variational-like inequality problem and vector optimization problem involving(G, α)-invex functions. Furthermore, we establish equivalence among the solutions of weak formulations of Minty vector variational-like inequality problem,Stampacchia vector variational-like inequality problem and weak efficient solution of vector optimization problem under the assumption of(G, α)-invex functions. Examples are provided to elucidate our results.     

Dissipative particle dynamics for complex geometries using non‐orthogonal transformation

Dissipative particle dynamics (DPD) was applied to fluid flow in irregular geometries using non‐orthogonal transformation, where an irregular domain is transformed into a simple rectangular domain. Transformation for position and velocity was used to relate the physical and computational domains. This approach was described by simulating fluid flow inside a two‐dimensional convergent–divergent nozzle. The nozzle geometry is controlled by the contraction ratio (CR) in the middle of the channel. The range of Reynolds number and CR, in this paper, was Re = 10hbox??200 and CR = 0.8 and 0.6, respectively. The DPD results were validated against in‐house computational fluid dynamic (CFD) finite volume code based on the stream function vorticity approach. The results revealed an excellent agreement between DPD and CFD. The maximum deviation between the DPD and CFD results was within 2%. Local and average coefficients of friction was calculated and it compared well with the CFD results. Copyright © 2011 John Wiley & Sons, Ltd.     

Pressure-induced phase transition and electronic properties of AlN nanowires: an ab initio study

The structural stability of AlN nanowires have been analyzed in wurtzite (B4), zincblende (B3), rocksalt (B1) and CsCl (B2) type phases using density functional theory based ab initio approach. The total energy calculations have been performed in a self-consistent manner using local density approximation as exchange correlation functional. The analysis finds the B4 type phase as most stable amongst the other phases taken into consideration and observes the structural phase transition from B4?→?B3, B4?→?B1, B4?→?B2, B3?→?B1 and B3?→?B2 at 42.7, 76.54, 142, 30.4 and 108.9?GPa respectively. Lattice parameter, bulk modulus and pressure derivatives of AlN nanowires have also been calculated for all the stable phases. The electronic band structure analysis of AlN nanowires shows a semiconducting nature in its B4, B3 and B1 type phases, whereas the B2 type phase is found to be metallic.     

Theoretical investigation of high-pressure phase transitions in Mg1-xSrxO

The stability of Mg_1-xSr_xO solid solution has been analyzed using charge transfer interaction potential (CTIP) model as well as density functional theory-based ab initio approach with Perdew–Burke–Ernzerhof (PBE) type parameterized generalized gradient approximation. The present CTIP model consists of long-range part as modified coulomb interactions and charge transfer forces whereas short-range part includes the van der Waals as well as Hafemeister Flygare type overlap repulsive interactions effective up to next nearest neighbor ions. The present study finds that under the influence of pressure host binary oxides as well as their solid solutions undergo B1→B2 structural phase transition in the pressure range of 54–495 GPa. The variation of ground state properties and transition pressures have also been analyzed as a function of Sr composition. The observed results for the end point members are in agreement to their experimental counterparts and the deviations have been discussed in terms of interactions taken into consideration in two approaches.     

On Semi-Finite Hexagons of Order (2, <Emphasis Type="Italic">t</Emphasis>) Containing a Subhexagon

The research in this paper was motivated by one of the most important open problems in the theory of generalized polygons, namely the existence problem for semi–finite thick generalized polygons. We show here that no semi–finite generalized hexagon of order (2, t) can have a subhexagon H of order 2. Such a subhexagon is necessarily isomorphic to the split Cayley generalized hexagon H(2) or its point–line dual H ^D (2). In fact, the employed techniques allow us to prove a stronger result. We show that every near hexagon \({\mathcal{S}}\) of order (2, t) which contains a generalized hexagon H of order 2 as an isometrically embedded subgeometry must be finite. Moreover, if \({H \cong H^{D}}\)(2) then \({\mathcal{S}}\) must also be a generalized hexagon, and consequently isomorphic to either H ^D (2) or the dual twisted triality hexagon T(2, 8).     

Binding Interactions in Copper,Silver and Gold π-Complexes

The copper(I), silver(I), and gold(I) metals bind π-ligands by σ-bonding and π-back bonding interactions. These interactions were investigated using bidentate ancillary ligands with electron donating and withdrawing substituents. The π-ligands span from ethylene to larger terminal and internal alkenes and alkynes. Results of X-ray crystallography, NMR, and IR spectroscopy and gas phase experiments show that the binding energies increase in the order Ag<Cu<Au and the binding energies are slightly higher for alkynes than for alkenes. Modulation of the electron density at the metal using substituents on the ancillary ligands shows that the π-back bonding interaction plays a dominant role for the binding in the copper and gold complexes.     

Rh(iii)-Catalyzed [5 + 1] annulation of 2-alkenylanilides and 2-alkenylphenols with allenyl acetates

Herein, we report a mild and highly regioselective Rh(iii)-catalyzed non-oxidative [5 + 1] vinylic C–H annulation of 2-alkenylanilides with allenyl acetates, which has been elusive so far. The reaction proceeds via vinylic C–H activation, regioselective 2,3-migratory insertion, β-oxy elimination followed by nucleophilic cyclization to get direct access to 1,2-dihydroquinoline derivatives. The strategy was also successfully extended to C–H activation of 2-alkenylphenols for constructing chromene derivatives. In the overall [5 + 1] annulation, the allene serves as a one carbon unit. The acetate group on the allene is found to be crucial both for controlling the regio- and chemoselectivity of the reaction and also for facilitating β-oxy elimination. The methodology was scalable and also further extended towards late stage functionalization of various natural products.

A highly regioselective Rh(iii)-catalyzed non-oxidative [5 + 1] vinylic C–H annulation of 2-alkenylanilides and 2-alkenylphenols with allenyl acetates was described for accessing dihyroquinoline and chromene derivatives.