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.     

Mineralogical analysis of auriferous ores from the El Diamante mine, Colombia

X-ray diffraction (XRD), Mössbauer spectrometry (MS), secondary ions mass spectroscopy (SIMS) and laser-ablation microprobe–inductively coupled plasma–mass spectrometry (LAM–ICP–MS) were used to study mineral samples of Colombian auriferous ores collected from the “El Diamante” mine, located in the municipality of Guachavez-Nariño, in Colombia. The samples were prepared as polished thin sections and polished sections. From XRD data, quartz, sphalerite and pyrite were detected and their respective cell parameters were estimated. From MS analyses, pyrite, arsenopyrite and chalcopyrite were identified; their respective hyperfine parameters and respective texture were deduced. Multiple regions of approximately 200 × 200 μm in each sample were analyzed with SIMS; the occurrence of “invisible gold” associated mainly with pyrite and secondarily with arsenopyrite could thus be assigned. It was also found that pyrite is of the arsenious type. Spots from 30 to 40 μm in diameter were analyzed with LAM–ICP–MS for pyrite, arsenopyrite and sphalerite; Au is “homogeneously” distributed inside the structure of the arsenious pyrite and the arsenopyrite (not as inclusions); the chemical composition indicates similarities of this “invisible gold”, forming a solid solution with arsenious pyrite and arsenopyrite. One hundred nineteen and 62 ppm of ‘invisible gold’ was quantified in 21 spots analyzed on pyrite and in 14 spots on arsenopyrite, respectively.     

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.

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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.     

Time-resolved fluorescence spectra using time-correlated photon counting: Picosecond fluorescence in aqueous solutions of Cr(III) complexes at room temperature

A new procedure for measuring time-resolved emission spectra has been implemented. This technique has subnanosecond time resolution combined with the sensitivity and dynamic range needed to cope with extremely weak luminescence. Using this method the emissions of Cr(NH₃)₂ (NCS)₄^? and Cr(NCS)₆^3- in aqueous solution at room temperature have each been analyzed into two components. The fast component has a broad spectrum and is assigned to prompt fluorescence with lifetime below 100 ps. The slow component is dominated by phosphorescence but may include some delayed fluorescence. The phosphorescence lifetime is 5.5 ± 0.5 ns in Cr(NH₃)₂ (NCS)₄^? and 1.65 ± 0.1 ns in Cr(NCS)₆^3-. Order of magnitude estimates have been derived for other photophysical parameters.     

Pentacyclic triterpenes from <Emphasis Type="Italic">Sarcostemma clausum</Emphasis>

A homologous series of alkanoic acid (C₂–C₅) esters of germanicol was isolated from the methanolic extract of Sarcostemma clausum, of which germanicol-3-propionate and 3-pentanoate have not been previously described in the literature. In addition, taraxasterol, multiflorenol, and bauerenol were also isolated for the first time from the genus Sarcostemma. Structures were elucidated by chemical and spectroscopic methods (NMR, IR, SM) and by comparison with literature data.Published in Khimiya Prirodnykh Soedinenii, No. 6 pp. 464–466, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.