Structural and electronic properties of hexa-adamantyl-hexa-phenylbenzene molecules studied by low temperature scanning tunneling microscopy

The electronic and structural properties of large molecules composed of a central hexa-phenylbenzene core surrounded by six adamantyl groups (Ad₆HPB) adsorbed on Ag(111) have been investigated using low temperature scanning tunneling microscopy (STM), adsorption and image calculations. On large 2D domains, the molecular organization displays two lattices. In one of them, molecules are slightly nested as a result of their relative flexibility during packing. These compounds also exhibit contrast variations in terms of used bias voltage in the self-assembled domains as well as in single molecule observations. This is attributed to the peculiar electronic properties of Ad₆HPB and to the role of peripheral groups.     

Alternative strategies for the stereoselective synthesis of enantioenriched 6-arylated piperidin-2-ones

Two alternative synthetic approaches to a variety of enantioenriched 6-arylated piperidin-2-ones have been developed. The first one is based on the hydrogenation of suitably arylated chiral cyclic enehydrazides. The second approach relies on the asymmetric catalytic hydrogenation of the corresponding N-alkylated precursors.     

Active Mamyshev regenerator

In this contribution, we numerically and experimentally investigate the extension of the so-called Mamyshev regenerator with the implementation of an additional Raman gain. We evaluate the potential efficiency and advantages of this new active Mamyshev regenerator at 40 Gbps and we highlight a strong reduction of the working power as well as a large improvement of the available output power.     

Solid-state electrochemical synthesis of ammonia: a review

Ammonia is one of the most produced chemicals worldwide, and it is not only a major end product but also an important energy storage intermediate. The solid-state electrochemical synthesis of ammonia has the promise to overcome the limitations of the conventional catalytic reactors such as the limited conversion, severe environmental pollution and high energy consumption. Solid-state electrolytes either protonic or oxide ion conductors have been reviewed and particular emphasis is placed on their application to synthesise ammonia. The highest rate of ammonia formation according to the type of electrolyte utilised were in the following order; solid polymers > Ce_0.8Gd_0.2O_2−δ-(Ca₃(PO₄)₂-K₃PO₄) composites > fluorites > perovskites > pyrochlores although the catalysts in electrodes also play an important role. The highest rate reported so far is found to be 1.13 × 10⁻⁸ mol s⁻¹ cm⁻² at 80 °C with a potential of 2 V using Nafion membrane, SmFe_0.7Cu_0.1Ni_0.2O₃ (SFCN), and Ni-Ce_0.8Sm_0.2O_2−δ as solid electrolyte, cathode and anode, respectively. Synthesising ammonia from steam and N₂, by-passing H₂ stage offers many advantages such as reduction of device numbers and then the overall costs. The factors affecting the rate of ammonia formation have been discussed as well.     

Synthesis of new iron–NHC complexes as catalysts for hydrosilylation reactions

A series of new piano‐stool iron(II) complexes comprising N‐heterocyclic carbene ligands [Fe(Cp)(CO)₂(NHC)]I (NHC = 1,3‐disubstituted imidazolidin‐2‐ylidene) have been synthesized and analyzed by ¹H NMR, ¹³C NMR, IR, elemental analysis and mass spectrometric techniques. These compounds were easily prepared from the reaction of disubstituted imidazolidin‐2‐ylidene with [FeI(Cp)(CO)₂] in toluene at room temperature. These complexes were tested in the catalytic hydrosilylation reaction of aldehydes and ketones with phenylsilane in solvent‐free conditions. After a basic hydrolysis step, the corresponding alcohols were obtained in good yields. Copyright © 2013 John Wiley & Sons, Ltd.     

Electronic Structure and Magnetic Anisotropy of an Unsaturated Cyclopentadienyl Iron(I) Complex with 15 Valence Electrons

The 15 valence-electron iron(I) complex [Cp^ArFe(IiPr₂Me₂)] ( 1 , Cp^Ar=C₅(C₆H₄-4-Et)₅; IiPr₂Me₂=1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene) was synthesized in high yield from the Fe^II precursor [Cp^ArFe(μ-Br)]₂. ⁵⁷Fe Mössbauer and EPR spectroscopic data, magnetic measurements, and ab initio ligand-field calculations indicate an S= 3/2 ground state with a large negative zero-field splitting. As a consequence, 1 features magnetic anisotropy with an effective spin-reversal barrier of U_eff=64 cm⁻¹. Moreover, 1 catalyzes the dehydrogenation of N,N-dimethylamine–borane, affording tetramethyl-1,3-diaza-2,4-diboretane under mild conditions.