Multiple silicon-hydrogen bond activations at adjacent rhodium and iridium centers

The reaction of 1 equiv of primary silanes, SiH(3)R (R = Ph, Mes), with [RhIr(CO)(3)(dppm)(2)] yields mono(silylene)-bridged complexes of the type [RhIr(H)(2)(CO)(2)(μ-SiHR)(dppm)(2)] (R = Ph or Mes), while for R = Ph the addition of 2 equiv yields the bis(silylene)-bridged complexes, [RhIr(CO)(2)(μ-SiHPh)(2)(dppm)(2)]. The kinetic isomer of this bis(silylene)-bridged product has the phenyl substituent axial on one silylene unit and equatorial on the other, and in the presence of excess silane this rearranges to the thermodynamically preferred "axial-axial" isomer, in which the phenyl substituents on each bridging silylene unit are axial and parallel to one another. The reaction of 1 equiv of diphenylsilane with [RhIr(CO)(3)(dppm)(2)] produces the mono(silylene)-bridged product, [RhIr(H)(2)(CO)(2)(μ-SiPh(2))(dppm)(2)], and the subsequent addition of silane in the presence of CO yields the silyl/silylene product [RhIr(H)(SiPh(2)H)(CO)(3)(κ(1)-dppm)(μ-SiPh(2))(dppm)]. The reaction of [RhIr(CO)(3)(dppm)(2)] with 2 equiv of SiH(2)Me(2) yields the analogous product [RhIr(H)(SiMe(2)H)(CO)(3)(κ(1)-dppm)(μ-SiMe(2))(dppm)]. Low-temperature NMR spectroscopic observation of some key intermediates, such as [RhIr(H)(SiH(2)Ph)(CO)(2)(μ-CO)(dppm)(2)], formed during the formation of the mono(silylene)-bridged species provides evidence for a mechanism involving initial Si-H bond activation at Rh, followed by the subsequent Si-H bond activation at Ir. The Si-H bond activation of a second equivalent of silane seems to be initiated by dissociation of the Rh-bound end of one diphosphine. The reaction of diphenylsilane with the cationic complex [RhIr(CH(3))(CO)(2)(dppm)(2)][CF(3)SO(3)] gives rise to a different reactivity pattern in which Si-H bond activation is initiated at Ir. In this case, the cationic silyl-bridged species, [RhIr(CH(3))(CO)(2)(κ(1):η(2)-SiHPh(2))(dppm)(2)][CF(3)SO(3)], contains an agostic Si-H interaction with Rh. In solution, at ambient temperature, this complex converts to two species, [RhIr(H)(COCH(3))(CO)(μ-H)(μ-SiPh(2))(dppm)(2)][CF(3)SO(3)] and [RhIr(CO)(2)(μ-H)(μ-SiPh(2))(dppm)(2)] [CF(3)SO(3)], formed by the competing methyl migration to CO and reductive elimination of methane, respectively. In the diphenylsilylene dihydride product, a weak interaction between the bridging silicon and the terminal Ir-bound hydride is proposed on the basis of NMR evidence.     

Enrichment,incorporation and oxidation of copper during anodising of aluminium–copper alloys

Porous anodic oxides generated on copper‐containing aluminium alloys are less regular than anodic oxides generated on pure aluminium. Specifically, a porous oxide morphology comprising layers of embryo pores, generated by a cyclic process of oxide film growth and oxygen evolution, is generally observed. In this work, the relation between the oxidation behaviour of copper during anodising and the specific porous oxide film morphology was investigated by electrochemical techniques, transmission electron microscopy and Rutherford backscattering spectroscopy (RBS). It was found that the anodising potential determines the oxidation behaviour of copper, and the latter determines the porous oxide morphology. At low voltage, relatively straight pores with continuous cell walls were obtained on Al? Cu alloys, but selective oxidation of aluminium atoms resulted in the occlusion of copper‐containing metallic nanoparticles in the anodic film. At higher potentials, copper oxidation promoted oxygen evolution within the barrier layer, and generation of a less regular film morphology. RBS, performed on Al? Cu alloy specimens, revealed a high volume fraction of copper atoms in the anodic films generated at low potentials and a reduced amount of copper atoms in the anodic oxide films generated at high potentials. Copyright © 2009 John Wiley & Sons, Ltd.     

Reactions of terminal polyynes with benzyl azide

Terminal di-, tri-, tetra-, and pentaynes substituted with a variety of functional groups react with benzyl azide in the presence of CuSO(4)·5H(2)O and ascorbic acid to give derivatives of 4-ethynyl-, 4-butadiynyl-, 4-hexatriynyl-, and 4-octatetraynyl-1,2,3-triazoles in moderate to good yields. These reactions appear to proceed regioselectively, and functionalization occurs exclusively at the terminal alkyne moiety. As well, no evidence of multiple azide additions to the polyyne framework is observed. X-ray crystallographic analysis of nine derivatives is used to document the regioselectivity of the reaction as well as outline structural characteristics of the 1,2,3-triazole products.     

The Effect of Nanoparticle Shape on the Photocarrier Dynamics and Photovoltaic Device Performance of Poly(3‐hexylthiophene):CdSe Nanoparticle Bulk Heterojunction Solar Cells

The charge separation and transport dynamics in CdSe nanoparticle:poly(3‐hexylthiophene) (P3HT) blends are reported as a function of the shape of the CdSe‐nanoparticle electron acceptor (dot, rod, and tetrapod). For optimization of organic photovoltaic device performance it is crucial to understand the role of various nanostructures in the generation and transport of charge carriers. The sample processing conditions are carefully controlled to eliminate any processing‐related effects on the carrier generation and on device performance with the aim of keeping the conjugated polymer phase constant and only varying the shape of the inorganic nanoparticle acceptor phase. The electrodeless, flash photolysis time‐resolved microwave conductivity (FP‐TRMC) technique is used and the results are compared to the efficiency of photovoltaic devices that incorporate the same active layer. It is observed that in nanorods and tetrapods blended with P3HT, the high aspect ratios provide a pathway for the electrons to move away from the dissociation site even in the absence of an applied electric field, resulting in enhanced carrier lifetimes that correlate to increased efficiencies in devices. The processing conditions that yield optimum performance in high aspect ratio CdSe nanoparticles blended with P3HT result in poorly performing quantum dot CdSe:P3HT devices, indicating that the latter devices are inherently limited by the absence of the dimensionality that allows for efficient, prolonged charge separation at the polymer:CdSe interface.     

The synthesis of Leishmania major phosphoglycan fragments

The triglycosyl monophosphate 1, heptaglycosyl triphosphates 2 and 3, and octaglycosyl triphosphate 4, which are fragments of the phosphoglycan part of Leishmania major lipo- and proteo-phosphoglycans have been prepared using di- and tri-saccharide H-phosphonates for construction of the phosphodiester bridges.     

Substituent effects on the disproportionation—combination rate constant ratios for gas‐phase halocarbon radicals,Part 5: Reactions of CF3 + CF3CH2CHCH3 and CF3CH2CHCH3 + CF3CH2CHCH3

Rate constant ratios, k_d/k_c for the disproportionation/combination reaction have been measured as 0.07 ± 0.02 when an H is removed from the CH₂ position of the CF₃CH₂CHCH₃ radical and as 0.24 ± 0.03 when the H is removed from the CH₃ position in the reaction with the CF₃ radical. For the self‐reaction between two CF₃CH₂CHCH₃ radicals, k_d/k_c has been measured as 0.27 ± 0.03 when the H is removed from the CH₂ position and as 0.47 ± 0.04 when the H is removed from the CH₃ position. The branching fraction, corrected for the number of hydrogens at each site, is 0.70 favoring the methyl position when the acceptor radical is CF₃ and 0.54 when CF₃CH₂CHCH₃ is the acceptor radical. Branching fraction results show that the CF₃ substituent on the CF₃CH₂CHCH₃ radical hinders disproportionation when CF₃ is the acceptor radical. When the accepting radical is CF₃CH₂CHCH₃ the CF₃ substituent may slightly impede the disproportionation reaction, but the branching ratio is nearly statistical. The effect of substituents on the donor radical, CF₃CH₂CHX, will be discussed for the series X = H, CF₃, Cl, and CH₃ when the acceptor radical is CF₃. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 549–557, 2001     

Actively stabilized single-frequency vertical-external-cavityAlGaAs laser

We report on actively stabilized single-frequency operation of a vertical-external-cavity surface-emitting semiconductor laser (VECSEL). The VECSEL was locked to a 300-MHz reference cavity allowing a relative frequency measurement that indicated a laser linewidth of 3 kHz. Coarse tuning over an 8.5-nm range was achieved, with fine tuning over 250 MHz. The laser produced up to 42 mW of output power in single-frequency operation     

A hydrogen-bonded adduct containing seven-component supramolecular aggregates

The title compound is a salt, 3,6,9,16,19,22-hexaaza­tri­cyclo­[22.2.2.2^11,14]­triaconta-1(26),11(29),12,14(30),24,27-hexa­ene–3,5-di­nitro­benzoic acid–methanol (1/4/2), C₂₄H₄₂N₆⁴⁺·4C₇H₃N₂O₆⁻·2CH₄O, in which the cation lies across a centre of inversion and one of the two independent anions is positionally disordered over two sets of atom sites having equal occupancy. The components are linked by four types of N—H⃛O hydrogen bond [N⃛O 2.674 (2)–2.815 (2) Å; N—H⃛O 149–163°] and one type of O—H⃛O hydrogen bond in which the acceptor is disordered over two closely adjacent sites [O⃛O 2.67 (4) and 2.75 (4) Å; O—H⃛O 172 and 173°], forming centrosymmetric seven-component aggregates.