Bench-Stable Dinuclear Mn(I) Catalysts in E-Selective Alkyne Semihydrogenation: A Mechanistic Investigation**

Dinuclear manganese hydride complexes of the form [Mn₂(CO)₈(μ-H)(μ-PR₂)] (R=Ph, 1 ; R=iPr, 2 ) were used in E-selective alkyne semi-hydrogenation (E-SASH) catalysis. Catalyst speciation studies revealed rich coordination chemistry and the complexes thus formed were isolated and in turn tested as catalysts; the results underscore the importance of dinuclearity in engendering the observed E-selectivity and provide insights into the nature of the active catalyst. The insertion product obtained from treating 2 with (cyclopropylethynyl)benzene contains a cis-alkenyl bridging ligand with the cyclopropyl ring being intact. Treatment of this complex with H₂ affords exclusively trans-(2-cyclopropylvinyl)benzene. These results, in addition to other control experiments, indicate a non-radical mechanism for E-SASH, which is highly unusual for Mn−H catalysts. The catalytically active species are virtually inactive towards cis to trans alkene isomerization indicating that the E-selective process is intrinsic and dinuclear complexes play a critical role. A reaction mechanism is proposed accounting for the observed reactivity which is fully consistent with a kinetic analysis of the rate limiting step and is further supported by DFT computations.     

Theoretical investigation of Q A −· -ligand interactions in bacterial reaction centers ofRhodobacter sphaeroides

Density functional theory was used to calculate magnetic resonance parameters for the primary stable electron acceptor anion radical (Q _A ^?· ) in its binding site in the bacterial reaction center (bRC) ofRhodobacter sphaeroides. The models used for the calculations of the Q _A ^?· binding pocket included all short-range interactions of the ubiquinone with the protein surroundings in a gradual manner and thus allowed a decomposition and detailed analysis of the different specific interactions. Comparison of the obtained hyperfine and quadrupole couplings with experimental data demonstrates the feasibility and reliability of calculations on such complex biologically relevant systems. With these results, the interpretation of previously published 3-pulse electron spin echo envelope modulation data could be extended and an assignment of the observed double quantum peak to a specific amino acid is proposed. The computations provide evidence for a slightly altered binding site geometry for the Q_A ground state as investigated by X-ray crystallography with respect to the Q _A ^t-· anion radical state as accessible via EPR spectroscopy. This new geometry leads to improved fits of the W-band correlated-coupled radical pair spectra of Q _A ^?· -P ₈₆₅ ^+· compared to orientation data from the crystal structure. Finally, a correlation of the¹⁴N quadrupole parameters of His219 with the hydrogen bond geometry and a comparison with previous systematic studies on the influence of hydrogen bond geometry on quadrupole coupling parameters (J. Fritscher: Phys. Chem. Chem. Phys. 6, 4950–4956, 2004) is presented.     

Phantom materials for single point imaging pulse sequences

The popularity of pure phase encode MRI techniques, including single point imaging (SPI), is steadily increasing, particularly in instances where the samples of interest are solid-like, or for other reasons possess short effective transverse relaxation times, T2*. As the interest in these techniques grows, so too does the need for a phantom material which is representative of this class of samples. The characteristics of such a phantom should include chemical and physical stability, straightforward preparation, high signal to noise ratio and relaxation times which are both easily manipulated and representative. To this end, we have developed a gelatin/sucrose-based gel which addresses the above criteria and behaves as a very flexible short T2* phantom. An order of magnitude variation in T1 and T2 can be achieved over a reasonable range of sucrose concentration. Even larger changes can be achieved with the addition of further doping agents.     

Spatial and temporal mapping of water content across Nafion membranes under wetting and drying conditions

Water transport and water management are fundamental to polymer electrolyte membrane fuel cell operation. Accurate measurements of water content within and across the Nafion layer are required to elucidate water transport behavior and validate existing numerical models.We report here a direct measurement of water content profiles across a Nafion layer under wetting and drying conditions, using a novel magnetic resonance imaging methodology developed for this purpose. This method, multi-echo double half k-space spin echo single point imaging, based on a pure phase encode spin echo, is designed for high resolution 1D depth imaging of thin film samples. The method generates high resolution (<8 μm) depth images with an SNR greater than 20, in an image acquisition time of less than 2 min. The high temporal resolution permits water content measurements in the transient states of wetting and drying, in addition to the steady state.     

Total synthesis of brasoside and littoralisone

The first total syntheses of littoralisone (1) and brasoside (2) have been achieved in 13 overall steps. Both natural products are forged from a common intermediate which is rapidly assembled using organocatalytic technology, including a proline-catalyzed alpha-aminoxylation and a contra-thermodynamic intramolecular Michael addition. Application of the two-step carbohydrate synthesis technology has enabled to access a selectively substituted glucose derivative for use as an intramolecular cycloaddition tether. This synthesis culminates with an intramolecular [2+2] photocycloaddition that serves to support the proposed biosynthetic origins of 1 from 2.