Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid-Assisted Reductive Coupling of Carbon Monoxide

Structure-function studies on the role of pendent Lewis acids in the reductive coupling of CO are reported. Cationic rhenium carbonyl complexes containing zero, one, or two phosphinoborane ligands (Ph_2P(CH_2)_nB(C_8H_(14)), n=1-3) react with the nucleophilic hydride [HPt(dmpe)_2]^+ to reduce [M-CO]^+ to M-CHO; this step is relatively insensitive to the Lewis acid, as both pendent (internal) and external boranes of appropriate acid strength can be used. In contrast, whether a second hydride transfer and C-C bond forming steps occur depends strongly on the number of carbon atoms between P and B in the phosphinoborane ligands, as well as the number of pendent acids in the complex: shorter linker chain lengths favor such reductive coupling, whereas longer chains and external boranes are ineffective. A number of different species containing partially reduced CO groups, whose exact structures vary considerably with the nature and number of phosphinoborane ligands, have been crystallographically characterized. The reaction of [(Ph -2P(CH_2)_2B(C_8H_(14)))_2Re(CO)4]^+ with [HPt(dmpe)_2]^+ takes place via a “hydride shuttle” mechanism, in which hydride is transferred from Pt to a pendent borane and thence to CO, rather than by direct hydride attack at CO. Addition of a second hydride in C_6D_5Cl at -40 ºC affords an unusual anionic bis(carbene) complex, which converts to a C-C bonded product on warming. These results support a working model for Lewis acid-assisted reductive coupling of CO, in which B (pendent or external) shuttles hydride from Pt to coordinated CO, followed by formation of an intramolecular B-O bond, which facilitates reductive coupling

Trialkylborane-Assisted CO_2 Reduction by Late Transition Metal Hydrides

Trialkylborane additives promote reduction of CO_2 to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO_2 to give a formateborane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO_2 reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formateborane adduct

Homogeneous CO Hydrogenation: Dihydrogen Activation Involves a Frustrated Lewis Pair Instead of a Platinum Complex

During a search for conditions appropriate for Pt-catalyzed CO reduction using dihydrogen directly, metal-free conditions were discovered instead. A bulky, strong phosphazene base forms a “frustrated” Lewis pair (FLP) with a trialkylborane in the secondary coordination sphere of a rhenium carbonyl. Treatment of the FLP with dihydrogen cleanly affords multiple hydride transfers and C−C bond formation

All fiber, low threshold, widely tunable single-frequency, erbium-doped fiber ring laser with a tandem fiber Fabry–Perot filter

An all fiber, widely tunable, single-frequency, erbium-doped fiber ring laser was constructed with a threshold pump power as low as 10 mW. Tuning over more than 30 nm was obtained by applying 0 to 17 dc V to an intracavity fiber Fabry–Perot filter. Threshold pump power versus wavelength data showed low variation over the tuning range. Mode hopping suppression with a tandem fiber Fabry–Perot filter is proposed and demonstrated. Stable single-frequency operation was demonstrated with side mode suppression higher than 35 dB

Mapping the Needs of Kinship Providers: A Mixed-Method Examination

This study utilized Concept Mapping (CM) to examine the needs of 105 kinship caregivers in one southeastern state, and to examine priority differences in conceptualization by placement type (formal vs. informal). CM is a mixed-method research methodology that employs multidimensional scaling and hierarchical cluster analyses to examine relationships among sets of data. Results indicate that kinship providers conceptualize needs via an eight-cluster solution, or concept map. As well, data suggest key priority differences between informal and formal caregivers in areas of financial, legal, and public outreach needs. After a brief review of literature about kinship care, this paper will explain results from the study, discuss findings in relation to previous works about kinship, and explicate practice, policy, education, and research implications derived from study findings

Thermodynamic Studies of [H_(2)Rh(diphosphine)_2]^+ and [HRh(diphosphine)_(2)(CH_(3)CN)]^(2+) Complexes in Acetonitrile

Thermodynamic studies of a series of [H_(2)Rh(PP)_2]^+ and [HRh(PP)_(2)(CH_(3)CN)]^(2+) complexes have been carried out in acetonitrile. Seven different diphosphine (PP) ligands were selected to allow variation of the electronic properties of the ligand substituents, the cone angles, and the natural bite angles (NBAs). Oxidative addition of H_2 to [Rh(PP)_2]^+ complexes is favored by diphosphine ligands with large NBAs, small cone angles, and electron donating substituents, with the NBA being the dominant factor. Large pK_a values for [HRh(PP)_(2)(CH_(3)CN)]^(2+) complexes are favored by small ligand cone angles, small NBAs, and electron donating substituents with the cone angles playing a major role. The hydride donor abilities of [H_(2)Rh(PP)_2]^+ complexes increase as the NBAs decrease, the cone angles decrease, and the electron donor abilities of the substituents increase. These results indicate that if solvent coordination is involved in hydride transfer or proton transfer reactions, the observed trends can be understood in terms of a combination of two different steric effects, NBAs and cone angles, and electron-donor effects of the ligand substituents

Efficiency of broadband four-wave mixing wavelength conversion using semiconductor traveling-wave amplifiers

We present a theoretical analysis and experimental measurements of broadband optical wavelength conversion by four-wave mixing in semiconductor traveling-wave amplifiers. In the theoretical analysis, we obtain an analytical expression for the conversion efficiency. In the experiments, both up and down-conversion efficiencies are measured as a function of wavelength shift for shifts up to 27 nm. The experimental data are well explained by the theoretical calculation. The observed higher conversion efficiency for wavelength down-conversion is believed to be caused by phase interferences that exist between various mechanisms contributing to the four-wave mixing process

Terahertz four-wave mixing spectroscopy for study of ultrafast dynamics in a semiconductor optical amplifier

Ultrafast dynamics in a 1.5-µm tensile-strained quantum-well optical amplifier has been studied by highly nondegenerate four-wave mixing at detuning frequencies up to 1.7 THz. Frequency response data indicate the presence of two ultrafast physical processes with characteristic relaxation lifetimes of 650 fs and <100 fs. The longer time constant is believed to be associated with the dynamic carrier heating effect. This is in agreement with previous time-domain pump-probe measurements using ultrashort optical pulses