Multiple-magnetic field 139La NMR and density functional theory investigation of the solid lanthanum(III) halides

Results from a solid-state ¹³⁹La NMR spectroscopic investigation of the anhydrous lanthanum(III) halides (LaX₃; X=F, Cl, Br, I) at applied magnetic fields of 7.0, 9.4, 11.7, 14.1, and 17.6 T are presented and highlight the advantages of working at high applied magnetic field strengths. The ¹³⁹La quadrupolar coupling constants are found to range from 15.55 to 24.0 MHz for LaCl₃ and LaI₃, respectively. The lanthanum isotropic chemical shifts exhibit an inverse halogen dependence with values ranging from −135 ppm for LaF₃ to 700 ppm for LaI₃, which represents nearly half of the total lanthanum chemical shift range. The spans of the magnetic shielding tensors also vary widely, from 35 to 650 ppm for the solid LaF₃ through LaI₃. DFT calculations of the ¹³⁹La electric field gradient and magnetic shielding tensors have been performed and provide a qualitative interpretation of the trends observed experimentally.     

The kinetics of propene and hexene polymerisation with [(SBI)ZrR]+X-: evidence for monomer-dependent early or late transition states

Whereas the rates of propene polymerisation catalysed by zirconocene ion pairs are strongly anion-dependent, hexene polymerisations are not; the findings demonstrate the existence of very different kinetic regimes for two closely related reactions.     

The Steinberg Lattice of a Finite Chevalley Group and its Modular Reduction

Let p be a prime and let q = p^a, where a is a positive integer.Let G 7equals; G(F_q) be a Chevalley group over F_q, with associatedsystem of roots and Weyl group W. Steinberg showed in 1957that G has an irreducible complex representation whose degreeequals the p-part of |G| [11]. This representation, now knownas the Steinberg representation, has remarkable properties,which reflect the structure of G, and there have been many researchpapers devoted to its study. The module constructed in [11]is in fact a right ideal in the integral group ring ZG of G,and is thus a ZG-lattice, which we propose to call the Steinberglattice of G. It should be noted that lattices not integrallyisomorphic to the Steinberg lattice may also afford the Steinbergrepresentation, and such lattices may differ considerably intheir properties compared with the Steinberg lattice.     

SENSITIZATION OF PHOTOREACTIONS IN EIMHJELLEN'S RHODOPSEUDOMONAS BY A PIGMENT ABSORBING AT 830 mμ*

Abstract— The excitation spectrum for bacteriochlorophyll b fluorescence, the action spectrum for cytochrome-553 oxidation, and the action spectrum for P-985 bleaching are compared to the absorption (1-T) spectrum of a Rhodopseudomonas sp. NHTC 133 extract over the range 770 to 930 mμ. These spectra show that a minor pigment P-830 is more effective in sensitizing cytochrome oxidation and P-985 bleaching than in exciting fluorescence of Bchl b. These results are consistent with the proposal that P-830 is a form of Bchl b in special relation to the reaction center pigment P-985.     

An Investigation of 1:1 Adducts of Gallium Trihalides with Triarylphosphines by Solid‐State 69/71Ga and 31P NMR Spectroscopy

Several 1:1 adducts of gallium trihalides with triarylphosphines, X₃Ga(PR₃) (X=Cl, Br, and I; PR₃=triarylphosphine ligand), were investigated by using solid‐state ^69/71Ga and ³¹P NMR spectroscopy at different magnetic‐field strengths. The ^69/71Ga nuclear quadrupolar coupling parameters, as well as the gallium and phosphorus magnetic shielding tensors, were determined. The magnitude of the ⁷¹Ga quadrupolar coupling constants (C_Q(⁷¹Ga)) range from approximately 0.9 to 11.0 MHz . The spans of the gallium magnetic shielding tensors for these complexes, δ₁₁?δ₃₃, range from approximately 30 to 380 ppm; those determined for phosphorus range from 10 to 40 ppm. For any given phosphine ligand, the gallium nuclei are most shielded for X=I and least shielded for X=Cl, a trend previously observed for In^III–phosphine complexes. This experimental trend, attributed to spin‐orbit effects of the halogen ligands, is reproduced by DFT calculations. The signs of C_Q(^69/71Ga) for some of the adducts were determined from the analysis of the ³¹P NMR spectra acquired with magic angle spinning (MAS). The ¹J(^69/71Ga,³¹P) and ΔJ(^69/71Ga, ³¹P) values, as well as their signs, were also determined; values of ¹J(⁷¹Ga,³¹P) range from approximately 380 to 1590 Hz. Values of ¹J(^69/71Ga,³¹P) and ΔJ(^69/71Ga,³¹P) calculated by using DFT have comparable magnitudes and generally reproduce experimental trends. Both the Fermi‐contact and spin‐dipolar Fermi‐contact mechanisms make important contributions to the ¹J(^69/71Ga,³¹P) tensors. The ³¹P NMR spectra of several adducts in solution, obtained as a function of temperature, are contrasted with those obtained in the solid state. Finally, to complement the analysis of NMR spectra for these adducts, single‐crystal X‐ray diffraction data for Br₃Ga[P(p‐Anis)₃] and I₃Ga[P(p‐Anis)₃] were obtained.     

In situ observations of water production and distribution in an operating H2/O2 PEM fuel cell assembly using 1H NMR microscopy

Proton NMR imaging was used to investigate in situ the distribution of water in a polymer electrolyte membrane fuel cell operating on H2 and O2. In a single experiment, water was monitored in the gas flow channels, the membrane electrode assembly, and in the membrane surrounding the catalysts. Radial gradient diffusion removes water from the catalysts into the surrounding membrane. This research demonstrates the strength of 1H NMR microscopy as an aid for designing fuel cells to optimize water management.     

Lessons for fragment library design: analysis of output from multiple screening campaigns

Over the past 8 years, we have developed, refined and applied a fragment based discovery approach to a range of protein targets. Here we report computational analyses of various aspects of our fragment library and the results obtained for fragment screening. We reinforce the finding of others that the experimentally observed hit rate for screening fragments can be related to a computationally defined druggability index for the target. In general, the physicochemical properties of the fragment hits display the same profile as the library, as is expected for a truly diverse library which probes the relevant chemical space. An analysis of the fragment hits against various protein classes has shown that the physicochemical properties of the fragments are complementary to the properties of the target binding site. The effectiveness of some fragments appears to be achieved by an appropriate mix of pharmacophore features and enhanced aromaticity, with hydrophobic interactions playing an important role. The analysis emphasizes that it is possible to identify small fragments that are specific for different binding sites. To conclude, we discuss how the results could inform further development and improvement of our fragment library. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

镱(Ⅲ)卟啉配合物的合成、结构表征和近红外光谱研究

合成了5个meso-位和β-位具有不同取代基的Yb(Ⅲ)卟啉配合物(2a~2e), 并对其结构进行了表征; 研究了配合物的可见光谱和近红外光谱性质, 测得了相关的量子产率和荧光寿命. 研究结果表明, 此类中性单核Yb(Ⅲ)卟啉配合物由于Yb³⁺的存在, 导致卟啉配体发生π→π*跃迁, 并将吸收的可见光能量传递给Yb³⁺的激发态, 使得配合物在近红外光区有很强的发光, 且meso-位为供电子基团的Yb(Ⅲ)卟啉配合物的发光效率比含吸电子基团的Yb(Ⅲ)卟啉配合物高, 而β-位溴化的Yb(Ⅲ)卟啉配合物的发光效率较差.     

Structural characterization of silver dialkylphosphite salts using solid‐state 109Ag and 31P NMR spectroscopy,IR spectroscopy and DFT calculations

High‐resolution solid‐state ¹⁰⁹Ag and ³¹P NMR spectroscopy was used to investigate a series of silver dialkylphosphite salts, Ag(O)P(OR)₂ (R = CH₃, C₂H₅, C₄H₉ and C₈H₁₇), and determine whether they adopt keto, enol or dimer structures in the solid state. The silver chemical shift, CS, tensors and |J(¹⁰⁹Ag, ³¹P)| values for these salts were determined using ¹⁰⁹Ag (Ξ = 4.652%) NMR spectroscopy. The magnitudes of J(¹⁰⁹Ag, ³¹P) range from 1250 ± 10 to 1318 ± 10 Hz and are the largest reported so far. These values indicate that phosphorus is directly bonded to silver for all these salts and thus exclude the enol structure. All ³¹P NMR spectra exhibit splittings due to indirect spin–spin coupling to ¹⁰⁷Ag (I = 1/2, NA = 51.8%) and ¹⁰⁹Ag (I = 1/2, NA = 48.2%). The ¹J(¹⁰⁹Ag, ³¹P) values measured by both ¹⁰⁹Ag and ³¹P NMR spectroscopy agree within experimental error. Analysis of ³¹P NMR spectra of stationary samples for these salts allowed the determination of the phosphorus CS tensors. The absence of characteristic P?O stretching absorption bands near 1250 cm^?1 in the IR spectra for these salts exclude the simple keto tautomer. Thus, the combination of solid‐state NMR and IR results indicate that these silver dialkylphosphite salts probably have a dimer structure. Values of silver and phosphorus CS tensors as well as ¹J(¹⁰⁹Ag, ³¹P) values for a dimer model calculated using the density functional theory (DFT) method are in agreement with the experimental observations. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthetic and computational studies of the palladium(iv) system Pd(alkyl)(aryl)(alkynyl)(bidentate)(triflate) exhibiting selectivity in C-C reductive elimination

Synthetic routes to methyl(aryl)alkynylpalladium(iv) motifs are presented, together with studies of selectivity in carbon-carbon coupling by reductive elimination from Pd(IV) centres. The iodonium reagents IPh(C[triple bond, length as m-dash]CR)(OTf) (R = SiMe(3), Bu(t), OTf = O(3)SCF(3)) oxidise Pd(II)Me(p-Tol)(L(2)) (1-3) [L(2) = 1,2-bis(dimethylphosphino)ethane (dmpe) (1), 2,2'-bipyridine (bpy) (2), 1,10-phenanthroline (phen) (3)] in acetone-d(6) or toluene-d(9) at -80 °C to form complexes Pd(IV)(OTf)Me(p-Tol)(C[triple bond, length as m-dash]CR)(L(2)) [R = SiMe(3), L(2) = dmpe (4), bpy (5), phen (6); R = Bu(t), L(2) = dmpe (7), bpy (8), phen (9)] which reductively eliminate predominantly (>90%) p-Tol-C[triple bond, length as m-dash]CR above ～-50 °C. NMR spectra show that isomeric mixtures are present for the Pd(IV) complexes: three for dmpe complexes (4, 7), and two for bpy and phen complexes (5, 6, 8, 9), with reversible reduction in the number of isomers to two occurring between -80 °C and -60 °C observed for the dmpe complex 4 in toluene-d(8). Kinetic data for reductive elimination from Pd(IV)(OTf)Me(p-Tol)(C[triple bond, length as m-dash]CSiMe(3))(dmpe) (4) yield similar activation parameters in acetone-d(6) (66 ± 2 kJ mol(-1), ΔH(?) 64 ± 2 kJ mol(-1), ΔS(?)-67 ± 2 J K(-1) mol(-1)) and toluene-d(8) (E(a) 68 ± 3 kJ mol(-1), ΔH(?) 66 ± 3 kJ mol(-1), ΔS(?)-74 ± 3 J K(-1) mol(-1)). The reaction rate in acetone-d(6) is unaffected by addition of sodium triflate, indicative of reductive elimination without prior dissociation of triflate. DFT computational studies at the B97-D level show that the energy difference between the three isomers of 4 is small (12.6 kJ mol(-1)), and is similar to the energy difference encompassing the six potential transition state structures from these isomers leading to three feasible C-C coupling products (13.0 kJ mol(-1)). The calculations are supportive of reductive elimination occurring directly from two of the three NMR observed isomers of 4, involving lower activation energies to form p-TolC[triple bond, length as m-dash]CSiMe(3) and earlier transition states than for other products, and involving coupling of carbon atoms with higher s character of σ-bonds (sp(2) for p-Tol, sp for C[triple bond, length as m-dash]C-SiMe(3)) to form the product with the strongest C-C bond energy of the potential coupling products. Reductive elimination occurs predominantly from the isomer with Me(3)SiC[triple bond, length as m-dash]C trans to OTf. Crystal structure analyses are presented for Pd(II)Me(p-Tol)(dmpe) (1), Pd(II)Me(p-Tol)(bpy) (2), and the acetonyl complex Pd(II)Me(CH(2)COMe)(bpy) (11).