Chemical bonding topology of ternary transition metal-centered bismuth cluster halides: from molecules to metals

The bismuth polyhedra in ternary transition metal-centered bismuth cluster halides may form discrete molecules or ions, infinite chains, and/or infinite layers. The chemical bonding in many of these diverse structures is related to that in deltahedral boranes exhibiting three-dimensional aromaticity by replacing the multicenter core bond in the boranes with two-center two-electron (2c-2e) bonds from the central transition metal to the nearest neighbor bismuth vertices. Examples of discrete molecules or ions include octahedral MBi(6)(micro-X)(12)(z)()(-) (X = Br, I; M = Rh, Ir, z = 3; M = Ru, z = 4) with exclusively 2c-2e bonds and pentagonal bipyramidal RhBi(7)Br(8) with a 5c-4e bond in the equatorial pentagonal plane indicative of M?bius aromaticity. The compound Ru(3)Bi(24)Br(20) contains a more complicated discrete bismuth cluster ion Ru(2)Bi(17)(micro-Br)(4)(5+), which can be dissected into a RuBi(5) closo octahedron and a RuBi(8) nido capped square antiprism bridged by a Ru(2)Bi(4)(micro-Br)(4) structural unit. In RuBi(4)X(2) (X = Br, I), the same Ru(2)Bi(4)(micro-Br)(4) structural unit bridges Bi(4) squares similar to those found in the known Zintl ion Bi(4)(2)(-) to give infinite chains of Ru(2)Bi(4) octahedra. The electron counts of the RuBi(5), RuBi(8), and Ru(2)Bi(4) polyhedra in these structures follow the Wade-Mingos rules. A different infinite chain structure is constructed from fused RhBi(7/2)Bi bicapped trigonal prisms in Rh(2)Bi(9)Br(3). This Rh(2)Bi(9)Br(3) structure can alternatively be derived from alternating Rh(2/2)Bi(4) octahedra and Rh(2/)(2)Bi(5) pentagonal bipyramids with electron counts obeying the Wade-Mingos rules. Related chemical bonding principles appear to apply to more complicated layer structures such as Pt(3)Bi(13)I(7) containing Kagomé nets of PtBi(8/2) cubes and Ni(4)Bi(12)X(3) containing linked chains of NiBi(6/3)Bi capped trigonal prisms.     

Arsenic Speciation in As(III)- and As(V)-Treated Soil Using XANES Spectroscopy

Arsenic (As) is a toxic trace element that occurs naturally in groundwater and soils. Understanding the reactions of arsenite (As(III)) and arsenate (As(V)) with soil and mineral surfaces is critical for predicting the fate and transport of As in the environment and developing better ways to remediate As-contaminated areas. This investigation uses X-ray absorption near edge spectroscopy (XANES) to evaluate the solid phase oxidation state and mineral surface binding sites in three agricultural soil samples from California, USA by fitting linear combinations of XANES spectra derived from several synthetic and well characterized As(III)- and As(V)-treated model compounds (Fe and Al metal hydroxides and aluminosilicate illite clay mineral). The results suggest that As(III) is either partially or completely oxidized to As(V) when reacted with soil in an aqueous, batch reaction. The As(III)-treated Aiken soil was composed of 60% As(III) attached to surfaces similar to lepidocrocite (γ-FeOOH)) and 40% As(V) attached to aluminosilicate (illite). The Fallbrook soil completely oxidized As(III) and the product was As(V) adsorbed on Al hydroxide (gibbsite, γ-Al(OH)₃) (62%), illite (16%), and lepidocrocite (γ-FeOOH) (22%). The reaction of As(III) with Wyo soil resulted in 42% As(III) adsorbed on surface similar to goethite and 58% As(V) adsorbed on lepidocrocite. Arsenic(V) adsorption on soil resulted in stable As(V) surface complexes that were well described by XANES spectra from As(V) adsorption complexes on gibbsite, illite, and lepidocrocite.     

Three-dimensional nonlinear optical chromophores based on metal-to-ligand charge-transfer from ruthenium(II) or iron(II) centers

In this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4' ':4',4' '-quaterpyridinium ligands. These complexes contain either Ru(II) or Fe(II) ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi* metal-to-ligand charge-transfer bands. The latter experiments reveal that these putatively octupolar D(3) chromophores exhibit two substantial components of the beta tensor which are associated with transitions to dipolar excited states. Computations involving time-dependent density-functional theory and the finite field method serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts.     

Solution redox chemistry of carbon nanotubes

UV/vis/NIR absorbance spectra were used to monitor electron transfer between small-molecule redox reagents and carbon nanotubes (CNTs). The oxidation of (6, 5)-enriched nanotubes in water with K(2)Ir(Cl)(6) reveals a valence electron density of 0.2-0.4 e(-)/100 carbon atoms and a reduction potential of approximately 800 mV versus NHE. The reduction potential of CNTs is found to increase with increasing band gap and to decrease with the introduction of an anionic dispersant. In light of this newly revealed redox chemistry of CNTs, we propose that the previously observed bleaching of the CNT absorbance spectrum at low pH is most likely a consequence of the oxidation of the nanotubes by oxygen. These results demonstrate facile oxidation and reduction of CNTs, provide a way to quantify the population of valence electrons, and point to possible applications of CNT in the catalysis of redox reactions.     

Effect of tip functionalization on transport through vertically oriented carbon nanotube membranes

Ionic flux through a composite membrane structure, containing vertically aligned carbon nanotubes crossing a polystyrene matrix film, was studied as a function of chemical end groups at the entrance to carbon nanotubes' (CNTs) cores. Plasma oxidation during the membrane fabrication process introduced carboxylic acid groups on the CNTs' tips that were modified using carbodiimide mediated coupling between the carboxylic acid and an accessible amine groups of the functional molecule. Functionalization molecules included straight chain alkanes, anionically charged dye molecules, and an aliphatic amine elongated by polypeptide spacers. Functionalization was confirmed by FTIR spectroscopy, and areal functional density was estimated by transmission electron microscopy studies of thiol terminated sites decorated by nanocrystalline gold. The transport through the membrane of two different sized but equally charged molecules (ruthenium bipyridine [Ru-(bipy)3(2+)] and methyl viologen [MV2+]) was quantified in a U-tube permeation cell by UV-vis spectroscopy. Relative selectivity of the permeates varied from 1.7 to 3.6 as a function of tip-functionalization chemistry. Anionic charged functional groups sharply increased the flux of the cationic permeates. This effect was reduced at higher solution ionic strength consistent with shorter Debye screening length. The observed selectivities were consistent with a hindered diffusion model with functionalization at the CNT tip and not along the length of the CNT core.     

Obtusin,a unique bromine-containing polycyclic ketal from the red marine alga Laurenciaobtusa

The structure of a unique bromine-containing ketal, obtusin ($\text{1}$), has been determined by spectral and X-ray crystallographic techniques. Obtusin is a natural component of the Mediteranean red alga $\text{Laurencia}$$\text{obtusa}$.     

Gel electrophoresis as a means of detecting ternary complex formation of thymidylate synthetase

Polyacrylamide gel electrophoresis was used to resolve as many as three protein components from incubation mixtures containing the inhibitor, 5-fluoro-2′-deoxyuridylate, the cofactor, 5,10-methylene tetrahydrofolate, and thymidylate synthetase. In a series of mixtures containing excess 5,10-methylenetetrahydrofolate and constant levels of thymidylate synthetase, the relative amounts of the protein components were shown to be dependent on the concentration of the inhibitor. Evidence is presented which suggests that the three protein components correspond to (1) native enzyme, (2) an inhibitor-cofactor-enzyme complex in a 1:1:1 molar ratio, and (3) an inhibitorcofactorenzyme complex in a 2:2:1 molar ratio, respectively. Ternary complexes of thymidylate synthetase are stable to gel filtration and are shown to undergo a relatively slow rate of breakdown on storage at 25 °C.     

Cluster chemistry: XXXIX. Gold—ruthenium clusters with sulphur ligands: Synthesis and structure of HRu3Au(μ3-S)(CO)9(PPh3), Ru3Au(μ3-SBut)(CO)9(PPh3) and Ru3Au2(μ3-S)(CO)9(PPh3)2

H₂Ru₃(μ₃-S)(CO)₉ is deprotonated by K[HBBu^s₃] to give cluster anions which react with [O{Au(PPh₃)}₃]⁺ or with AuCl(PPh₃)/T1⁺ to give HRu₃Au(μ₃-S)(CO)₉(PPh₃) (1) and Ru₃Au₂(μ₃-S)(CO)₉(PPh₃)₂ (3). A similar sequence with HRu₃(μ₃-SBu^t)(CO)₉ leads to Ru₃Au(μ₃-SBu^t)(CO)₉(PPh₃) (2) as the main product although some 1 also forms, indicating SC cleavage competes with deprotonation of HRu₃(μ₃-SBu^t)(CO)₉ by [HBBu^s₃]^?. The X-ray crystal structures of 1, 2 and 3 are described; (1) and (2) have “butterfly” AuRu₃ cores with markedly different hinge angles of 119 and 148° respectively, while 3 has a trigonal-bipyramidal Au₂Ru₃ skeleton. All three clusters have the sulphur atom symmetrically bridging the Ru₃ triangular face.     

The stereochemistry of guggulsterol-1

The steroechemistry of guggulsterol-1, a component of the exudate of $\text{Commiphora}$$\text{mukul}$, is shown to be 20(R), 22(R)($\text{3}$).     

Chiral conflict. The effect of temperature on the helical sense of a polymer controlled by the competition between structurally different enantiomers: from dilute solution to the lyotropic liquid crystal state

Helical polymers appended with paired structurally different enantiomers, which have opposing helical sense preferences, yield a new kind of relationship between optical activity and temperature, and also reveal unusual details of the nature of chiral interactions. Consistent with a statistical physical theory developed for these experiments, the proportion of the competing chiral groups, determined by synthesis, fixes the compensation temperature at which the helical senses are equally populated. The lyotropic liquid crystal state formed by these polymers yields therefore a nematic state at any chosen temperature over a very wide range, with a cholesteric state arising with tightening pitch as temperature deviates from this point. Far from the nematic temperature, the pitch reaches the nanometer scale and therefore the reflection of visible light. Before crossing zero at the nematic temperature, the optical activity becomes so large that it may be observed with the unaided eye through crossed polarizers.