Reactivity of molybdenum and rhenium hydroxo-carbonyl complexes toward organic electrophiles

The hydroxo compounds [Re(OH)(CO)(3)(N-N)] (N-N=bipy, 2 a; Me(2)-bipy, 2 b) were prepared in a biphasic H(2)O/CH(2)Cl(2) medium by reaction of [Re(OTf)(CO)(3)(N-N)] with KOH. In contrast, when anhydrous CH(2)Cl(2) was used, the binuclear hydroxo-bridged compound [[Re(CO)(3)(bipy)](2)(mu-OH)]OTf (3-OTf) was obtained. Compound [Re(OH)(CO)(3)(Me(2)-bipy)] (2 b) reacted with phenyl acetate or vinyl acetate to afford [Re(OAc)(CO)(3)(Me(2)-bipy)] (4) and phenol or acetaldehyde, respectively. The reactions of [Mo(OH)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1), 2 a, and 2 b toward several unsaturated organic electrophiles were studied. The reaction of 1 with (p-tolyl)isocyanate afforded an adduct of N,N'-di(p-tolyl)urea and the carbonato-bridged compound [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(mu-eta(1)(O),eta(1)(O)-CO(3))] (5). In contrast, the reaction of 2 a with phenylisocyanate afforded [Re(OC(O)NHPh)(CO)(3)(bipy)] (6); this results from formal PhNCO insertion into the O-H bond. On the other hand, compounds [Mo[SC(O)NH(p-tolyl)](eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (7), [Re[SC(O)NH(p-tolyl)](CO)(3)(Me(2)-bipy)] (8 a), and [Re[SC(O)NHEt](CO)(3)(Me(2)-bipy)] (8 b) were obtained by reaction of 1 or 2 b with the corresponding alkyl or aryl isothiocyanates. In those cases, RNCS was inserted into the M-O bond. The reactions of 1, 2 a, and 2 b with dimethylacetylenedicarboxylate (DMAD) gave the complexes [Mo[C(OH)-C(CO(2)Me)C(CO(2)Me)-O](eta(3)-C(3)H(4)-Me-2)(CO)(phen)] (9) and [Re[C(OH)C(CO(2)Me)C(CO(2)Me)O](CO)(2)(N-N)] (N-N=bipy, 10 a; Me(2)-bipy, 10 b). The molecules of these compounds contain five-membered metallacycles that are the result of coupling between the hydroxo ligand, DMAD, and one of the CO ligands. The new compounds were characterized by a combination of IR and NMR spectroscopy, and for [[Re(CO)(3)(bipy)(2)(mu-OH)]BF(4) (3-BF(4)), 4, 5, 6, 7, 8 b, 9, and 10 b, also by means of single-crystal X-ray diffraction.     

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.     

Two Intercalation Mechanisms of Oxazole Yellow Dimer (YOYO-1) into DNA

The oxazole yellow dye, YOYO-1 (a symmetric homodimer), is a commonly used molecule for staining DNA. We applied the brightness analysis to study the intercalation of YOYO-1 into the DNA. We distinguished two binding modes of the dye to dsDNA: mono-intercalation and bis-intercalation. Bis-intercalation consists of two consecutive mono-intercalation steps, characterised by two distinct equilibrium constants (with the average number of base pair per binding site equals 3.5): K1=3.36±0.43×107M−1 and K2=1.90±0.61×105M−1, respectively. Mono-intercalation dominates at high concentrations of YOYO-1. Bis-intercalation occurs at low concentrations.     

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.     

Synthesis and photophysical evaluations of β-fused uracil-porphyrin derivatives

New β-fused uracil-porphyrin conjugates were synthesized by the tetramerization of uracil-pyrroles under acidic conditions. Two different synthetic approaches were systematically studied in order to evaluate their efficiency, as well as the possibility to obtain a single regioisomer. Metallation effects were studied for aggregation in solution, and preliminary photophysical experiments were also performed in order to evaluate the potential of these new compounds.     

Contribution of thermal imaging to fertigation in soilless culture

Thermography is a tool used in many scientific disciplines, including agriculture. This paper describes the application of thermography as a rapid diagnostic method of adequate watering. Two experiments were conducted. In experiment 1, Philodendron erubescens and Anthurium andraeum were transplanted to pots in a greenhouse in Almeria (Spain). The vegetative growth parameters of these plants were measured. In experiment 2, two areas of vegetative cover were established on green walls: one with a combination of aromatic plants and another with ornamental indoor plants. The thermographic images were recorded using a compact infrared camera, which had a spectral infrared range of 7.3–13 μm, microbolometer of 320 × 240 pixels, and the resolution was 0.01 °C at 30 °C. Three irrigation treatments were applied in both experiments, consisting of a control treatment (CT), a deficit irrigation [1/3 less volume, deficient irrigation (DI)] treatment, and an excess irrigation [1/3 greater volume, excess irrigation (EI)] treatment. In both experiments, the sample temperatures were recorded by thermography for each irrigation treatment. In experiment 1, the vegetative growth parameters were greater under CT than under DI or EI. The data of the reference thermographs over the leaves of the potted plants were significantly correlated with the superior growth parameters under the optimal irrigation treatment. A continuous vegetative canopy was formed on both of the green walls in experiment 2, and the average temperatures were correlated with the irrigation treatments in this experiment. The temperatures reflected in the reference thermographs allowed for the determination of the most appropriate irrigation treatment. These results suggest that thermography can be a useful method to provide an early diagnosis of water stress in potted plants and green walls.