Molybdenum(VI) Bis(imido) Complexes: From Frustrated Lewis Pairs to Weakly Coordinating Cations

Molybdenum(VI) bis(imido) complexes [Mo(NtBu)₂(L^R)₂] (R=H 1 a ; R=CF₃ 1 b ) combined with B(C₆F₅)₃ ( 1 a /B(C₆F₅)₃, 1 b /B(C₆F₅)₃) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H₂ and Et₃SiH affords ion pairs [Mo(NtBu)(NHtBu)(L^R)₂][HB(C₆F₅)₃] (R=H 2 a ; R=CF₃ 2 b ) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H₂O leads to [Mo(NtBu)(NHtBu)(L^R)₂][(HO)B(C₆F₅)₃] (R=H 3 a ; R=CF₃ 3 b ). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a . Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C₆F₅)₃]⁻. We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(L^R)₂][{PhCH₂O}B(C₆F₅)₃] (R=H 4 a ; R=CF₃ 4 b ). Catalysis occurs at [HB(C₆F₅)₃]⁻ while [Mo(NtBu)(NHtBu)(L^R)₂]⁺ (R=H or CF₃) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC).     

Effects of hydrophobic polyhedral oligomeric silsesquioxane coating on water vapour barrier and water resistance properties of paperboard

The substitution of fossil based packaging materials with materials from renewable sources is a topic of current interest. Polyhedral oligomeric silsesquioxanes with fatty acid moieties can have a renewable content of more than 90 % and are therefore called bio-POSS. In this study the bio-POSS octa-(ethyl erucamide) silsesquioxane was coated on a paperboard substrate as a liquid coating. The water resistance and the water vapour barrier properties of the paperboard were improved. Samples on which the bio-POSS coating layer was dried at 80 °C had a slightly higher water resistance and water vapour barrier than samples dried at room temperature. UV treatment of the coating layer had little effect. Solid state ¹H-NMR of UV treated coatings showed no reaction of double bonds of bio-POSS in the coating layer. Multiple coating considerably enhanced the water resistance and water vapour barrier properties of the paperboard, due to an increase in the coating thickness and a reduction in number of pores on top coated surfaces.     

Cobalt‐Catalyzed Cross‐Coupling of Functionalized Alkylzinc Reagents with (Hetero)Aryl Halides

A combination of 10 % CoCl₂ and 20 % 2,2′‐bipyridine ligands enables cross‐coupling of functionalized primary and secondary alkylzinc reagents with various (hetero)aryl halides. Couplings with 1,3‐ and 1,4‐substituted cycloalkylzinc reagents proceeded diastereoselectively leading to functionalized heterocycles with high diastereoselectivities of up to 98:2. Furthermore, alkynyl bromides react with primary and secondary alkylzinc reagents providing the alkylated alkynes.     

Development of novel composite sorbents for the removal of actinides from environmental and analytical solutions

A novel approach to preparing granular sorbents for the separation of actinides has been developed, where the extractant is directly immobilized in an inert matrix. This allows substantially higher extractant loadings in the sorbent than for conventional extraction chromatography resins. This approach utilizes polyacrylonitrile (PAN) as the inert matrix material. The well-known actinide extractant octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) has been loaded into sorbent granules at extractant loadings from 20 to 33 wt.% CMPO. The porosity of the PAN matrix allows the active material to have rapid and complete access to the solution containing the impurities, resulting in improved kinetics and higher sorption capacities. Sorbents containing CMPO were prepared using PAN as a binding matrix, and tested against commercially available actinide extraction chromatography resins. Direct comparative batch contact tests performed with TRU-Resin^Ò and CMPO-PAN using an INEEL tank waste simulant, resulting in distribution coefficient (K _d) values for Am approximately 2-90 times higher for CMPO-PAN than for TRU-Resin. Batch distribution coefficient (K _d) values for Pu were approximately 60-150 times higher for CMPO-PAN than for the TRU-Resin. Acid dependency curves were generated for Am and Pu with CMPO-PAN over a concentration range of 1 mM to 5M HNO₃.     

Regiospecific Intramolecular Aldol Condensation Induced by Conjugate Addition of lithium dimethylcuprate to ζ-Oxo-α, β-enones preliminary communication [1]

ζ-Oxo-α, β-enones react with lithium dimethylcuprate to give cyclic aldols such as hydroxydecalone 1 and hydroxyspiro[4.5]decanone 2 in a regio- and stereospecific manner. This new reaction, a combination of conjugate methyl addition to α, β-enones with directed intramolecular aldolisation, is suggested to proceed via either enoate anions, such as 8 and 11 , or radical anions, such as 9 → 10 and 12 → 13 , as intermediates.     

Pump-induced nonlinear refractive-index change in erbium- and ytterbium-doped fibers: theory and experiment

A 980-nm pump-induced nonlinear refractive-index (n2) change in erbium-doped (20-m) and ytterbium-doped (20-m) fibers has been measured at 1064 nm by time-delayed photorefractive beam coupling in a co-propagating and counterpropagating geometry. It was found that n2 decreases at the wavelength of the probe beam when the pump beam is present. We present a semiclassical theory based on a four-state system that accounts for the pump-induced change of n2. Both theoretical and experimental results show that a significant index change, of the order of 10%, can be obtained for cw pump powers as small as 10 mW.     

Forces between a single atom and its distant mirror image

An excited-state atom whose emitted light is backreflected by a distant mirror can experience trapping forces, because the presence of the mirror modifies both the electromagnetic vacuum field and the atom's own radiation reaction field. We demonstrate this mechanical action using a single trapped barium ion. We observe the trapping conditions to be notably altered when the distant mirror is translated across an optical wavelength. The well-localized barium ion enables the spatial dependence of the forces to be measured explicitly. The experiment has implications for quantum information processing and may be regarded as the most elementary optical tweezers.     

Effects of gemini surfactants on egg phosphatidylcholine bilayers in the fluid lamellar phase

The influence of 1,4-butanediamonium-N,N'-dialkyl-N,N,N',N'-tetramethyl dibromides (CmA, m = 7-16 is the number of alkyl carbons) on the egg yolk phosphatidylcholine (EYPC) bilayer thickness and lipid surface area at the bilayer-aqueous phase interface is studied using X-ray diffraction on fluid lamellar CmA + EYPC + H2O phases as a function of CmA:EYPC and H2O:EYPC molar ratios and the alkyl chain length m. At the constant CmA:EYPC = 0.4 and H2O:EYPC = 18 molar ratios, the CmA induced bilayer thickness decrease shows a minimum and the lipid surface area increase a maximum at the alkyl chain length m = 9. The obtained results are discussed in the context of a structural perturbation model of the cut-off effect in biological potencies of surfactants which occurs when increasing the alkyl substituent chain length above the critical value.     

New approach to the measurement of the nonlinear refractive index of short (<25 m) lengths of silica and erbium-doped fibers

The nonlinear refractive index n2 of silica fiber (24 m) and erbium-doped fiber (10 m) is measured to within an accuracy of 5% by use of time-delayed photorefractive beam coupling of intense 53-ps, 1.064-microm pulses that experience self-phase modulation in the fibers. The resultant induced grating autocorrelation response yields a value of n2/A(eff) and a calibration standard for the fiber. A phase shift of the order of 0.19pi can be detected and is limited only by laser amplitude fluctuations. A unique advantage of this technique is its ability to measure n2 accurately in short lengths (z < or = 25 m) of fiber, whereas other approaches typically use much longer lengths of fiber (z > or = 100 m).