Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

Finite-dimensional Leavitt path algebras

We classify the directed graphs E for which the Leavitt path algebra L(E) is finite dimensional. In our main results we provide two distinct classes of connected graphs from which, modulo the one-dimensional ideals, all finite-dimensional Leavitt path algebras arise.     

Electrochemical characterization of composite membranes based on crown-ethers intercalated into montmorillonite

Oxyethylene macrocyclic compounds (crown-ethers) act as ligands of intracrystalline cations of certain layered silicates as montmorillonites. Stable intercalation materials are formed which are used to prepare organic-inorganic membranes by encapsulating these intercalation compounds with a poly-butadiene thin coating. Electrochemical Impedance Spectroscopy (EIS) is used to study the resulting composite membranes in contact with aqueous electrolytes. From the impedance plots, the ionic resistance of the membranes is obtained. The thickness of the polybutadiene coating is an important factor determining the ability of ions to pass across the membrane. Marked differences in the ionic resistance are observed as a function of the nature of the interlayer macrocyclic compound. For non-intercalated montmorillonite membranes, the ionic resistance is strongly reduced, whereas for some crown-ether intercalated materials such as 18-crown-6 and dibenzo 24-crown-8, iono-selective membranes are obtained. Concerning the nature of the electrolyte, cations exhibiting greater hydration energies show higher difficulties to pass through the membrane and, consequently, the ionic resistance increases.     

Higher order shock waves

Shock waves and the relevant Rankine-Hugoniot conditions may be inadequate even in simple cases. As an example, the electromagnetic field generated by a point charge, whose velocity jumps from0 to a constant value, not only jumps across a spherical surface expanding at light speed, but also includes a-distribution term. This suggests that the concept of higher order shock waves be introduced, the associated compatibility conditions being also deduced.

---

Sommario Il concetto di onda d'urto può rivelarsi inadeguato per descrivere situazioni anche semplici. A titolo di esempio, si determina esplicitamente l'espressione del campo elettromagnetico generato da una carica puntiforme la cui velocità passa istantaneamente da0 a un valore costante. Il campo elettromagnetico non solo è discontinuo attraverso una superficie sferica che si espande alla velocità della luce, ma include anche un termine che coinvolge la distribuzione. Ciò suggerisce di definire le onde d'urto di ordine superiore, per le quali si determinano le corrispondenti condizioni di compatibilità.

     

The modulating possibilities of dicarbollide clusters: optimizing the Kharasch catalysts

exo-Cluster dicarbollides substitution has allowed tuning of the E degrees (Ru(II)/Ru(III)) potential to obtain the best-performing Kharasch catalyst. We postulate that this is possible through the to-and-fro electron movement between the boron cluster and the sulfonium moieties.     

Theoretical study on the adsorption of aromatic compounds on platinum clusters

B3 LYP hybrid functional with LACVP* pseudopotential was applied for the optimization of geometries of complexes resulting from interaction of benzene, pyridine, naphthalene, and quinoline with Pt_n (n = 4, 7) clusters. For benzene‐containing complexes, the most stable form corresponds to a bridge adsorption, with benzene undergoing considerable geometric distortions, assuming a boat‐like conformation. C? H bonds are bended upward from the plane of the cluster. C? C bonds stretch, especially when they form π‐complexes with low coordinated Pt atoms. Some arrangements for pyridine complexes involving the N atom of the organic moiety undergo further distortions, apparently preserving a formal C? N π bond. Except for that distortion, the behavior of any heteroaromatic complex is similar to that of benzene in the same arrangement. The quinoline–Pt₇ complex can suitably be used for simulation of the cinchonidine (CD) anchorage over Pt. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003