Light olefin production from CO/H2 over silica supported Fe/Mn/K catalysts derived from a bimetallic carbonyl anion, [Fe2Mn(CO)12]?

Fe/Mn/K catalysts derived from support of the anionic carbonyl, [Fe₂Mn(CO)₁₂]^– on silica were compared with catalysts prepared by aqueous impregnation methods, and found to be more selective for production of C₂–C₄ olefins. Addition of K had little effect, whereas variations in reaction conditions altered selectivity owing to secondary reactions of the alkene products.

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Fe/Mn/K, , [Fe₂Mn(CO)₁₂]^–, , , , C₂–C₄. , , .

     

Synthesis of C2-symmetric trans-2,6-diarylpiperidinones via aryl cuprate addition: an unexpected stereochemical outcome

An efficient procedure for the preparation of trans-2,6-diaryl piperidinones has been developed. Addition of aryl Grignard reagents to 2-aryl dihydropyridones under catalytic copper promoted conditions generates the trans isomer exclusively, an unprecedented stereochemical event. The X-ray structures of both starting material and product have been solved and shed light on the steric constraints and substrate geometry leading to the observed product. The reaction conditions tolerate a variety of aromatic nucleophiles to generate C₂-symmetric products in good overall yields.     

Assembly of Photosystem I and II during the Early Phases of Light-Induced Development of Chloroplasts from Proplastids in Spirodela oligorrhiza

The aquatic higher plant Spirodela oligorrhiza , which contains proplastids when grown in the dark, was used to study light-dependent chloroplast development. Low-temperature (77 K) and room temperature fluorescence were utilized in situ on whole plants to examine plastid development. The dark-grown plants contain two 77 K fluorescence peaks, at 633 nm (F633) and at 657 nm (F657), with F633 dominating. The F657 species represents protochlorophyllide that is bound to protochloro-phyllide oxidoreductase. It was rapidly phototrans-formed to chlorophyllide (within 5 s) via a monomolec-ular reaction. Free protochlorophyllide (F633) was converted to chlorophyllide during a 3 h exposure to light. Photosystem (PS) assembly in Spirodela could be detected 2 h after the plants were first exposed to light, with the PSII reaction center (77 K fluorescence at 684 nm) appearing slightly before the PSI reaction center (77 K fluorescence at 725 nm). After the first reaction centers were formed the antenna complexes were added; the light-harvesting complex (LHC) I of PSI appeared after 8 h, and 47 kDa chlorophyll protein of PSII appeared between 12 h and 24 h. After 30 h of exposure to light, the plants acquired the ability to perform a light state transition, marking the appearance of functional LHCII complexes in the developing chloroplast. Finally, it was found that photosynthetic activity, as measured by room temperature chlorophyll fluorescence, accelerated con-comitantly with detection of the antenna complexes. Therefore, although reaction centers are detected very early during the proplastid to chloroplast conversion, they may have little activity or be unstable until the antennae are present.     

Reaction rates for O + HD → OH + D and O + HD → OD + H

We have calculated reaction rates for the reactions O + HD → OH + D and O + DH → OD + H using improved canonical variational transition state theory and least-action ground-state transmission coefficients with an ab initio potential energy surface. The kinetic isotope effects are in good agreement with experiment. The optimized tunneling paths and properties of the variational transition states and the rate enhancement for vibrationally excited reactants are also presented and compared with those for the isotopically unsubstituted reaction O + H₂ → OH + H. The thermal reactions at low and room temperature are predicted to occur by tunneling at extended configurations, i.e., to initiate early on the reaction path and to avoid the saddle point regions. Tunneling also dominates the low and room temperature reactions for excited vibrational states, but in these cases the results are not as sensitive to the nature of the tunneling path. Overbarrier mechanisms dominate for both thermal and excited-vibrational state reactions for T > 600 K. For the excited-state reaction (with initial vibrational quantum number n > 0) a transition state switch occurs for T > 1000 K for the O + HD(n = 1) → OD + H case and for T > 1500 K for the O + DH(n = 1) → OD + H reaction, and this may be a general phenomenon for excited-state reactions at higher temperature. In the present case the switch occurs from an early variational transition state where the vibrationally adiabatic approximation is expected to be valid to a tighter variational transition state where nonadiabatic effects are probably important and should be included.     

Further reactions of some bis(vinylidene)diruthenium complexes

Whereas {Ru(dppm)Cp*}₂(μ-CCCC) (2) is the only product formed by deprotonation of [{Ru(dppm)Cp*}₂{μ(CCHCHC)}]⁺ with dbu, a mixture of 2 with Ru{CCCHCH(PPh₂)₂[RuCp*]}(dppm)Cp* (3) and {Cp*Ru(PPh₂CHCCH-)}₂ (4) is obtained with KOBu^t. A similar reaction with [{Ru(dppm)Cp*}₂{μ(CCMeCMeC)}]⁺ (5) gave Ru{CCCMeCH(PPh₂)₂[RuCp*]}(dppm)Cp* (6). X-ray structures of 4, 5 and 6 confirm the presence of the 1-ruthena-2,4-diphosphabicyclo[1.1.1]pentane moiety, which is likely formed by an intramolecular attack of the deprotonated dppm ligand on C(1) of the vinylidene ligand. Protonation of {Ru(dppe)Cp*}₂(μ-CCCC) (8-Ru) regenerates its precursor [{Ru(dppe)Cp*}₂{μ(CCHCHC)}]²⁺ (7-Ru). Ready oxidation of the bis(vinylidene) complex affords the cationic carbonyl [Ru(CO)(dppe)Cp*]PF₆ (9) (X-ray structure).     

A novel high-performance fourier transform ion cyclotron resonance cell for improved biopolymer characterization

A new trapped ion cell design for use with Fourier transform ion cyclotron resonance mass spectrometry is described. The design employs 15 cylindrical ring electrodes to generate trapping potential wells and 32 separately assignable rod electrodes for excitation and detection. The rod electrodes are positioned internal to the ring electrodes and provide excitation fields that are thereby linearized along the magnetic field over the entire trapped ion volume. The new design also affords flexibility in the shaping of the trapping field using the 15 ring electrodes. Many different trapping well shapes can be generated by applying different voltages to the individual ring electrodes, ranging from quadratic to linearly ramped along the magnetic field axis, to a shape that is nearly flat over the entire trap volume, but rises very steeply near the ends of the trap. This feature should be useful for trapping larger ion populations and extension of the useful range of ion manipulation and dissociation experiments since the number of stages of ion manipulation or dissociation is limited in practice by the initial trapped ion population size. Predicted trapping well shapes for two different ring electrode configurations are presented, and these and several other possible configurations are discussed, as are the predicted excitation fields based on the use of rod electrodes internal to the trapping ring electrodes. Initial results are presented from an implementation of the design using a 3.5 T superconducting magnet. It was found that ions can be successfully trapped and detected with this cell design and that selected ion accumulation can be performed with the utilization of four rods for quadrupolar excitation. The initial results presented here illustrate the feasibility of this cell design and demonstrate differences in observed performance based upon different trapping well shapes.     

Cluster Chemsitry. 96. Penta- and hexa-nuclear ruthenium cluster complexes derived from reactions of cyclopentadienes with Ru5(μ5-C2PPh2)(μ-PPh2)(CO)13

The reactions between Ru₅( ₅-C₂PPh₂)(gm-PPh₂(CO)₁₃ (1) and cyclopentadienes afforded the hexanuclear clusters Ru₆( ₆-C)( ₃-PPh₂)₂(CO)₁₀(-C₅ R ₅) [R ₅ = H₅ (2), H₄Me (3), Me₅ (4)] which contain an encapsulated carbide and a face-capping ₃-CH group, formed by cleavage of CC and CP bonds of the C₂PPh₂ moiety in1. In the reaction with cyclopentadiene, the unusual ligand C₁₃H₁₂O, formed by combination of C₂, CO and two molecules of C₅H₆ (or one molecule of dicyclopentadien), was characterized in the complex Ru₅( ₄-PPh) ( ₄-C₁₃H₁₂O)(-PPh₂(CO)₁₁(-C₅H₅) (5). In the reaction with pentamethylcyclopentadiene, the vinylidene complex Ru₅( ₃-CCHPh)( ₄-PPh)( ₄-PPh) (-PPh₂)(CO)₉(-C₅Me₅) (6) was also formed.     

Structure of γ-Li3AsO4 by High Temperature Powder Neutron Diffraction

The structure of γ-Li₃AsO₄ has been refined by Rietveld analysis of high resolution powder neutron diffraction data collected at 770 and 850°C. The structure is related to that of γ-Li₃PO₄, being a distorted hexagonal close-packed arrangement of oxide ions with half the tetrahedral sites filled by cations. Arsenic occupies the same sites as phosphorus in γ-Li₃PO₄, Li⁺ ions show positional disorder; Li(1) ions are split into central and off-center positions within their tetrahedral sites; Li(2) ions are distributed over pairs of face sharing tetrahedral sites at 850°C while occupying only one site at 770°C. The powder neutron data show anisotropic broadening of hkl peaks with h = 2n + 1. The broadening has been accounted for using a modified Rietveld code. The broadened peaks correspond to those reflections that are not common to the related low temperature β-phase and are associated with a doubling of the a-axis during the β-γ transition. The origin of the broadening is the small size of the γ-phase domains in the a -direction; adjacent domains are probably connected by antiphase boundaries.     

Development of a sensitive enzyme immunoassay for the detection of phenyl-β-d-thioglucuronide in human urine

Immunoassays for the measurement of glucuronides in human urine can be a helpful tool for the assessment of human exposure to toxic chemicals. Therefore an enzyme immunoassay (EIA) for the specific detection of phenyl-β-d-thioglucuronide was developed. The immunoconjugate was formed by coupling p-aminophenyl-β-d-thioglucuronide to the carrier protein thyroglobulin leaving an exposed glucuronic acid. The hapten-protein conjugate was adsorbed to gold colloids in order to enhance the immunogenic effect. Rabbits were injected with the immunogold conjugates to raise polyclonal antibodies. The resulting competitive assay showed an inhibition by phenyl-β-d-thioglucuronide at sample concentrations of 23.0 ± 1.3 ng/mL (50% B/B₀) and a high cross-reactivity to p-aminophenyl-β-D-thioglucuronide (120%). Little cross-reactivities (< 2%) were observed for potential urinary cross reactants. In addition human urine samples were incubated with β-glucuronidase in order to investigate the EIA for specific matrix effects. An integration of high-performance liquid chromatography (HPLC) and EIA was developed in an attempt to decrease the matrix effects and increase the sensitivity of the overall method. The hyphenated technique HPLC-EIA may be used to monitor human exposure to toxic thiophenol which is excreted by mammals as urinary phenyl thioglucuronide.     

Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems

The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBu^t) of [Ru(NCCH₂CN)(PPh₃)₂Cp]PF₆ (1) gives Ru{NCCH(CN)}(PPh₃)₂Cp (2), which adds a second [Ru(PPh₃)₂Cp]⁺ unit to give [{Ru(PPh₃)₂Cp}₂(μ-NCCHCN)]⁺ (3). Attempted deprotonation of the latter to give the μ-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{NCC(CN)₂}(PPh₃)₂Cp (4) and [{Ru(PPh₃)₂Cp}₂{μ-NCC(CN)CN}]PF₆ (5), and with pentacyanopropenide, Ru{NCC(CN)C(CN)C(CN)₂}(PPh₃)₂Cp (6) and [{Ru(PPh₃)₂Cp}₂{μ-NCC(CN)C(CN)C(CN)CN}]PF₆ (7). The Ru(dppe)Cp* analogues of 6 and 7 (8 and 9) were also prepared. Thermolysis of 6 (refluxing toluene, 12 h) results in loss of PPh₃ and formation of the binuclear cyclic complex {Ru(PPh₃)Cp[μ-NC{C(CN)C(CN)₂}CN]}₂ (10). The solid-state structures of 2-4 and 8-10 have been determined and the nature of the isomers shown to be present in solutions of the binuclear cations 7 and 9 by NMR studies has been probed using Hartree-Fock and density functional theory.