Synthesis of 1,2-di-(4-pyridyl)ethylenediamine and related compounds

Hydrolysis of N,N'-diacyl-1,2-di(4-pyridyl)ethylenediamines 1 in aqueous sulfuric acid gave the corresponding imidazolines 3. 1,2-Di-(4-pyridyl)ethylenediamine 2 was prepared in 61 % yield by treating N,N'-di-t-butyl-oxycarbonyl-1,2-di(4-pyridyl)ethylenediamine 4 with trifluoroacetic acid or in 94% yield by the hydrolysis under basic conditions of N,N'-diphthaloylglycyl-1,2-di(4-pyridy)ethylenediamine 13.     

C-H activations at iridium(I) square-planar complexes promoted by a fifth ligand

In the presence of ligands such as acetonitrile, ethylene, or propylene, the Ir(I) complex [Ir(1,2,5,6-eta-C8H12)(NCMe)(PMe3)]BF4 (1) transforms into the Ir(III) derivatives [Ir(1-kappa-4,5,6-eta-C8H12)(NCMe)(L)(PMe3)]BF4 (L = NCMe, 2; eta2-C2H4, 3; eta2-C3H6, 4), respectively, through a sequence of C-H oxidative addition and insertion elementary steps. The rate of this transformation depends on the nature of L and, in the case of NCMe, the pseudo-first-order rate constants display a dependence upon ligand concentration suggesting the formation of five-coordinate reaction intermediates. A similar reaction between 1 and vinyl acetate affords the Ir(III) complex [Ir(1-kappa-4,5,6-eta-C8H12){kappa-O-eta2-OC(Me)OC2H3}(PMe3)]BF4 (7) via the isolable five-coordinate Ir(I) compound [Ir(1,2,5,6-eta-C8H12){kappa-O-eta2-OC(Me)OC2H3}(PMe3)]BF4 (6). DFT (B3LYP) calculations in model complexes show that reactions initiated by acetonitrile or ethylene five-coordinate adducts involve C-H oxidative addition transition states of lower energy than that found in the absence of these ligands. Key species in these ligand-assisted transformations are the distorted (nonsquare-planar) intermediates preceding the intramolecular C-H oxidative addition step, which are generated after release of one cyclooctadiene double bond from the five-coordinate species. The feasibility of this mechanism is also investigated for complexes [IrCl(L)(PiPr3)2] (L = eta2-C2H4, 27; eta2-C3H6, 28). In the presence of NCMe, these complexes afford the C-H activation products [IrClH(CH=CHR)(NCMe)(PiPr3)2] (R = H, 29; Me, 30) via the common cyclometalated intermediate [IrClH{kappa-P,C-P(iPr)2CH(CH3)CH2}(NCMe)(PiPr3)] (31). The most effective C-H oxidative addition mechanism seems to involve three-coordinate intermediates generated by photochemical release of the alkene ligand. However, in the absence of light, the reaction rates display dependences upon NCMe concentration again indicating the intermediacy of five-coordinate acetonitrile adducts.     

Infrared spectrum of benzene in bromine and carbon tetrachloride solutions

The benzene—bromine complex at room temperature has been re-studied by infrared with bromine in excess of benzene. Solutions of 0.225 M benzene in bromine—carbon tetrachloride mixtures were studied. Under this condition, the spectral changes of measurable benzene absorption bands were observed more clearly than previously. The out-of-plane vibrations of benzene were observed to shift to higher frequencies. The equilibrium constant was found to be 0.11 ? mole^?1. The accord with the equilibrium constant derived from benzene rich systems supports the concept of a specific interaction. A C_6V symmetry is favoured for the geometry of the complex.     

Noether's Theorem on Surfaces

In this article we prove a version of Noether's Theorem (of Calculus of Variations) which is valid for a general regular (compact) surface. As a special feature, the Lie group of transformations is allowed to act on the Cartesian product of the surface and the functional space. Additionally, we apply the Theorem to a problem in Classical Differential Geometry of surfaces. The given application is actually an example showing how Noether's Theorem can be used to construct invariant properties of the solutions to variational problems defined on surfaces, or equivalently, of the solutions to the associated Euler-Lagrange equations resulting from them.     

Periodic solutions for second order singular damped differential equations

We study the existence of positive periodic solutions for second order singular damped differential equations by combining the analysis of the sign of Green?s functions for the linear damped equation, together with a nonlinear alternative principle of Leray–Schauder. Recent results in the literature are generalized and significantly improved.     

Dual Nucleophilic Substitution Reactions of O,O‐Diethyl 2,4‐dinitrophenyl Phosphate and Thionophosphate Triesters

The reactions of the title compounds with phenoxides, secondary alicyclic (SA) amines, and pyridines, in 44 wt% ethanol–water, at 25°C and an ionic strength of 0.2 M, were subjected to kinetic and product studies. From analytical techniques (HPLC and NMR), two pathways were detected (nucleophilic attack at the phosphoryl center and at the C‐1 aromatic carbon) for the reactions of all the nucleophiles with the phosphate ( 2 ) and for the pyridinolysis of the thionophosphate ( 1 ). Only aromatic nucleophilic substitution was found for the reactions of 1 with phenoxides and SA amines. For the dual reactions, the nucleophilic rate constants (k_N) were separated in two terms: $k_{\rm N}^{\rm P}$ and $k_{\rm N}^{{\rm Ar}}$, which are the rate constants for the corresponding electrophilic centers. The absence of a break in the Brønsted‐type plots for the attack at P is consistent with concerted mechanisms. The Brønsted slopes, β_Ar 0.32–0.71, for the attack at the aromatic C‐1, are in agreement with stepwise mechanisms where formation of a Meisenheimer complex is the rate‐determining step. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 202–211, 2013     

WATER MOVEMENT CAUSED BY SPREADING SURFACTANTS IN UNSATURATED SYSTEMS OF PARTICLES OF NONUNIFORM SIZE

The movement of water originated by the spreading of two surfactants was analyzed in glass beads as well as on soil systems, both of particles of nonuniform size

The higher difference of surface tension produced in the system by 1 -hexadecanol compared to that of 1-tetradecanol led therefore to a higher amount of water moved. Decreased proportion of the smaller sized particles in glass beads system produced a decrease in the total water moved by both surfactants.

Organic matter acted in soil as a second surfactant in glass beads. This effect was compared in glass beads systems once 1-hexadecanol was evenly distributed among the particles as continuous film, which played a role alike that of organic matter in soil and then a second surfactant 1-tetradecanol was added. These additional surfactant effect diminished the difference between initial and final surface tension (surface tension depression) of the system and so the total water moved.

The soil organic matter (1.7%) modified the water movement curve in the presence of low (0.2g) content of 1-hexadecanol, whereas for high content of either alcohol (0.4g) or low content of 1-tetradecanol content (0.2g) the water movement curves were the same     

On the Number of Type Change Loci of a Generalized Complex Structure

In this note, we describe a procedure to construct generalized complex structures whose type change locus has arbitrarily many path components on products of the circle with a connected sum of closed 3-manifolds. As an application, we use the procedure to exhibit such geometric structures on a myriad of simply connected 4-manifolds among many others.