Detection and Characterization of Hydride Ligands in Iron Complexes by High-Resolution Hard X-ray Spectroscopy and Implications for Catalytic Processes.

Two hydride catalysts [Fe(CO)(dppp)H(NO)] (dppp = 1,3-bis(diphenylphosphino)propane) and [Fe(CO)H(NO)(PPh3)2] in comparison with nonhydride analogues [Fe(dppe)(NO)2] (dppe = 1,3-bis(diphenylphosphino)ethane) and [Fe(NO)2(PPh3)2] are investigated with a combination of valence-to-core X-ray emission spectroscopy (VtC-XES) and high-energy resolution fluorescence detected X-ray absorption near-edge structure (HERFD-XANES). To fully understand the experiments and to obtain precise information about molecular levels being involved in the spectral signals, time-dependent density functional theory (TD-DFT) calculations and ground state density functional theory (DFT) calculations are necessary. An excellent agreement between experiment and theory allows the identification of particular spectral signals of the Fe-H group. Antibonding Fe-H interactions clearly contribute to pre-edge signals in HERFD-XANES spectra, while bonding Fe-H interactions cause characteristic signatures in the VtC-XES spectra. The sensitivity of both methods with respect to the Fe-H distance is demonstrated by a scanning simulation approach. The results open the way to study metal hydride complexes in situ, their formation, and their fate during catalytic reactions, using high-resolution XANES and valence-to-core X-ray emission spectroscopy.

Route to Highly Substituted Pyridines.

Pyridine rings are common structural motifs found in a number of biologically active compounds, including some top-selling pharmaceuticals. We have developed a new approach to access substituted pyridines. The method aims to provide a reliable synthesis of a diverse range of substituted pyridines through a three-step procedure. Readily available enones are first converted into 1,5-dicarbonyls through a two-step Hosomi-Sakurai allylation/oxidative cleavage sequence, which is followed by subsequent cyclization to the corresponding pyridine using hydroxylamine hydrochloride. A variety of substituted pyridines have been synthesized using this method.

The electronic ground state of [Fe(CO)3 (NO)](-) : a spectroscopic and theoretical study.

During the past 10 years iron-catalyzed reactions have become established in the field of organic synthesis. For example, the complex anion [Fe(CO)3 (NO)](-) , which was originally described by Hogsed and Hieber, shows catalytic activity in various organic reactions. This anion is commonly regarded as being isoelectronic with [Fe(CO)4 ](2-) , which, however, shows poor catalytic activity. The spectroscopic and quantum chemical investigations presented herein reveal that the complex ferrate [Fe(CO)3 (NO)](-) cannot be regarded as a Fe(-II) species, but rather is predominantly a Fe(0) species, in which the metal is covalently bonded to NO(-) by two π-bonds. A metal-N σ-bond is not observed.

Fe-catalyzed allylic C-C-bond activation: vinylcyclopropanes as versatile a1,a3,d5-synthons in traceless allylic substitutions and [3 + 2]-cycloadditions.

The low-valent iron complex Bu(4)N[Fe(CO)(3)(NO)] (TBAFe) catalyzes the allylic C-C-bond activation of electron-poor vinyl cyclopropanes to generate synthetically useful a1,a3,d5-synthons which are prone to undergo multiple consecutive reactions. The versatility of this approach is demonstrated by a traceless allylic substitution and a formal [3 + 2] cycloaddition to give either functionalized acyclic products or densely substituted cyclopentanes and pyrrolidines in high yields and regioselectivities.

Fe-catalyzed multicomponent reactions: the regioselective alkoxy allylation of activated olefins and its application in sequential Fe catalysis.

We present herein a versatile and broadly applicable Fe-catalyzed regioselective alkoxy allylation of activated double bonds. Substituted allylic carbonates are converted into the corresponding σ-enyl Fe complexes by reaction with Bu(4)N[Fe(CO)(3)(NO)] (TBAFe) at 30 °C. The liberated alkoxide adds to an activated double bond with the generation of a C-nucleophile, which is trapped by the σ-enyl Fe complex in a regioselective manner. Alternatively, the alkoxide acts as a base in deprotonating an external pronucleophile, which undergoes Michael addition. The method is characterized by a broad functional group tolerance, mild reaction conditions, low catalyst loadings, and high regioselectivities in favor of the ipso-substitution product.

Binuclear Fe-complexes as catalysts for the ligand-free regioselective allylic sulfenylation.

Binuclear Fe-complexes that are readily prepared by treating Bu(4)N[Fe(CO)(3)(NO)] with an excess of thiol or from Fe-salts under reductive conditions are potent catalysts for the regioselective allylic sulfenylation. Low catalyst loadings of only 0.25 mol% and reaction temperatures of only 40 °C allow for the coupling of functionalized allylic starting materials with functionalized mercaptans in good yield with full retention of the configuration.

Measuring the nanomechanical properties of cancer cells by digital pulsed force mode imaging.

In this paper, we demonstrate that the digital pulsed force mode data can distinguish two cancer cell lines (HeLa, Panc) by their mechanical properties. The live cells were imaged in buffer solution. The digital pulsed force mode measured 175 force-distance curves per second which, due to the speed of the measurement, were distorted by the viscous drag in the buffer. We show that this drag force causes a sinusoidal addition to the force-distance curves. By subtracting the viscous drag effect one obtains standard force-distance curves. The force-distance curves are then evaluated to extract key data on the curves, such as adhesion energies, local stiffness or the width of the hysteresis loop. These data are then correlated to classify the force-distance curves. We show examples based on the width of the hysteresis loop and the adhesion energies. Outliers in this classification scheme are points where, potentially, interesting new physics or different physics might happen. Based on classification schemes adapted to experimental settings, we propose that the digital pulsed force mode is a tool to evaluate the time evolution of the mechanical response of cells.

Cyclic peroxides derived from the marine sponge Plakortis simplex.

Two new cyclic peroxides, 2 and 3, were isolated from a sample of the Norwegian sponge Plakortis simplex. Their structures including relative stereochemistry were elucidated by interpretation of MS and NMR data. Compound 3 exhibited moderate in vitro activity against six solid human tumor cell lines with IC50 values in the range 7-15 microg/mL.