Alkyne coupling at a rhenium-monocarborane substrate: synthesis of Re,B-eta2:sigma-butadienyl complexes

Treatment of 7-NH(2)Bu(t)-nido-7-CB(10)H(12) in tetrahydrofuran (THF) with LiBu(n)(3 equiv) and then [ReBr(CO)(3)(THF)(2)] gives the rhenacarborane dianion [1-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-ReCB(10)H(10)](2-), isolated as the bis-[N(PPh(3))(2)](+) salt (4). Iodine oxidation of this Re(I) intermediate gives the Re(III) complex [1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-ReCB(10)H(10)] 6 in which the carborane functions formally as an 8-electron (6pi+ 2sigma) donor. Reaction of with ligands L in the presence of Me(3)NO gives substituted products [1,2-mu-NHBu(t)-2,2-(CO)(2)-2-L-closo-2,1-ReCB(10)H(10)][L = PPh(3)(7a), CNXyl (7b; Xyl = C(6)H(3)Me(2)-2,6), or Bu(t)C triple bond CH (7c)]. Formation of complex 7c is unexpectedly accompanied by [1,2-mu-NHBu(t)-2,2-(CO)(2)-3,2-sigma:eta(2)-{C(=CHBu(t))-CH=CHBu(t)}-closo-2,1-ReCB(10)H(9)] 8a, in which an alkyne-derived dienyl group is bound to both the rhenium centre and to an adjacent boron vertex. Complex 8a is also obtained from 7c with Bu(t)C triple bond CH and Me(3)NO. The same reaction of 7c, using PhC triple bond CH or CNXyl instead of Bu(t)C triple bond CH, gives, respectively, [1,2-micro-NHBu(t)-2,2-(CO)(2)-3,2-sigma:eta(2)-{C(=CHBu(t))-CH=CHPh}-closo-2,1-ReCB(10)H(9)] 8b and [1,2-micro-NHBu(t)-2-Bu(t)C triple bond CH-2-CO-2-CNXyl-closo-2,1-ReCB(10)H(10)] 9. Addition of donors L to results in displacement from rhenium of the pendant dienyl moiety, yielding [1,2-mu-NHBu(t)-2,2-(CO)(2)-2-L-3-{C(=CHBu(t))-CH=CHBu(t)}-closo-2,1-ReCB(10)H(9)][L = PMe(3)(10a), CNBu(t)(10b)]. Single-crystal X-ray diffraction analyses have confirmed the novel structural features of compounds 6, 7c, 8b and 9.     

Tandem differential mobility spectrometry with chemical modification of ions

A tandem ion mobility spectrometer with two sequential differential mobility spectrometry (DMS) drift tubes and with detectors at ambient pressure is described and modes of operation are demonstrated. Separate but coordinated electronic control for each drift tube allows several modes of operation including: all ions passing; compensation voltage (CV) scanning; and ion selection over a narrow CV range. Any of these modes can be applied to each drift tube allowing several combinations of analytical measurements, analogous to tandem mass spectrometry, with ions entered into a gas atmosphere containing reagents between the mobility regions. Ions may be changed by cluster or displacement reactions and characterized in the second DMS analyzer. Proton bound dimers of compounds appearing near 0?V CV in DMS1 were isolated in DMS1, introduced into 1?% isopropanol vapors, and resolved at characteristic CV values in the DMS2. This is achieved with analyzer dimensions little greater than a single DMS instrument.     

Using monomer properties to obtain integrated intensities for vibrational transitions of van der Waals complexes

The integrated intensities of vibrational transitions depend on the magnitude of the derivatives of the dipole with respect to nuclear motion. Normally, the only reliable way to compute such derivatives is by tedious and expensive ab initio calculations. In this paper, we present a simplification for weakly bound complexes based on distributed schemes for describing the charge densities and polarizabilities of the monomers. Formulations based on both Cartesian and spherical harmonics are presented. The results for both these schemes agree exactly with each other, and qualitatively with full ab initio calculations for the hydrogen fluoride dimer, (HF)₂.     

The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline‐Catalyzed Oxidation of Alkyl Halides to Aldehydes

An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis.     

Self-assembled alkanethiol structures on gold: A further insight into the origins of structural rearrangement phenomena

Self-assembled structures of alkanethiols that have been deposited on gold from ethanolic solutions are susceptible to both chemical and physical changes: ethanol provides a medium for the formation of S-alkyl hydrogen thiocarbonates and related compounds via reaction with dissolved, atmospheric, CO₂. Deposition from ethanolic solutions results in multilayered structures incorporating these compounds, which at room temperature are susceptible to time-dependent structural rearrangement and molecular migration.     

Dalitz analysis of D0-->K(0)(S)pi(+)pi(-)

In e(+)e(-) collisions using the CLEO detector, we have studied the decay of the D0 to the final state K(0)(S)pi(+)pi(-) with the initial flavor of the D0 tagged by the decay D(*+)-->D0pi(+). We use the Dalitz technique to measure the resonant substructure in this final state and clearly observe ten different contributions by fitting for their amplitudes and relative phases. We observe a K(*)(892)(+)pi(-) component which arises from doubly Cabibbo suppressed decays or D0-D0; mixing.     

Observation of B-->K(0)(S)pi(+)pi(-) and Evidence for B-->K(*+/-)pi(-/+)

We report on a search for charmless hadronic B decays to the three-body final states K(0)(S)h(+)pi(-), K(+)h(-)pi(0), K(0)(S)h(+)pi(0) (h(+/-) denotes a charged pion or kaon), and their charge conjugates, using 13.5 fb(-1) of integrated luminosity produced near sqrt[s]=10.6 GeV, and collected with the CLEO detector. We observe the decay B-->K0pi(+)pi(-) with a branching fraction (50(+10)(-9)(stat.)+/-7(syst.))x10(-6) and the decay B-->K(*+)(892)pi(-) with a branching fraction (16(+6)(-5)(stat.)+/-2(syst.))x10(-6).     

Toward a structural understanding of turbulent drag reduction: nonlinear coherent states in viscoelastic shear flows

Nontrivial steady flows have recently been found that capture the main structures of the turbulent buffer layer. We study the effects of polymer addition on these "exact coherent states" (ECS) in plane Couette flow. Despite the simplicity of the ECS flows, these effects closely mirror those observed experimentally: Structures shift to larger length scales, wall-normal fluctuations are suppressed while streamwise ones are enhanced, and drag is reduced. The mechanism underlying these effects is elucidated. These results suggest that the ECS are closely related to buffer layer turbulence.