1,10‐Phenanthroline and Non‐Symmetrical 1,3,5‐Triazine Dipicolinamide‐Based Ligands For Group Actinide Extraction

The synthesis and evaluation of new extractants for spent nuclear fuel reprocessing are described. New bitopic ligands constituted of phenanthroline and 1,3,5‐triazine cores functionalized by picolinamide groups were designed. Synthetic routes were investigated and optimized to obtain twelve new polyaza‐heterocyclic ligands. In particular, an efficient and versatile methodology was developed to access non‐symmetric 2‐substituted‐4,6‐di(6‐picolin‐2‐yl)‐1,3,5‐triazines from the 1,3,5‐triazapentadiene precursor in the presence of anhydride reagents. Extraction studies showed the ability of both ligand series to extract and separate actinides selectively at different oxidation states (U^VI, Np^V,VI, Am^III, Cm^III, and Pu^IV) from an acidic solution (3 M HNO₃). Phenanthroline‐based ligands show the most promising efficiency for use in the group actinide extraction (GANEX) process due to a higher number of donor nitrogen atoms and a suitable pre‐organization of the dipicolinamide‐1,10‐phenanthroline architecture.     

Rollover‐Assisted C(sp2)C(sp3) Bond Formation

Rollover cyclometalation involves bidentate heterocyclic donors, unusually acting as cyclometalated ligands. The resulting products, possessing a free donor atom, react differently from the classical cyclometalated complexes. Taking advantage of a “rollover”/“retro‐rollover” reaction sequence, a succession of oxidative addition and reductive elimination in a series of platinum(II) complexes [Pt(N,C)(Me)(PR₃)] resulted in a rare C(sp²)?C(sp³) bond formation to give the bidentate nitrogen ligands 3‐methyl‐2,2′‐bipyridine, 3,6‐dimethyl‐2,2′‐bipyridine, and 3‐methyl‐2‐(2′‐pyridyl)‐quinoline, which were isolated and characterized. The nature of the phosphane PR₃ is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of C?H bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize.     

Trinuclear Gold Clusters Supported by Cyclic (alkyl)(amino)carbene Ligands: Mimics for Gold Heterogeneous Catalysts

The synthesis of air‐ and moisture‐stable trinuclear mixed‐valence gold(I)/gold(0) clusters is described. They promote the catalytic carbonylation of amines under relatively mild conditions. The synthetic route leading to the trinuclear clusters involves a simple ligand exchange from the readily available μ³‐oxo‐[(Ph₃PAu)₃O]⁺ complex. This synthetic method paves the way for the preparation of a variety of mixed‐valence gold(I)/gold(0) polynuclear clusters. Moreover, the well‐defined nature of the complexes demonstrates that the catalytic process involves a rare example of a definite change of oxidation state of gold from Au⁰₂Au^I to Au^I₃.     

Skeleton Decoration of NHCs by Amino Groups and its Sequential Booster Effect on the Palladium‐Catalyzed Buchwald–Hartwig Amination

A challenging synthetic modification of PEPPSI‐type palladium pre‐catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald–Hartwig amination. This is illustrated, for example, by the quantitative amination of 4‐chloroanisole by morpholine within 2 h at 25 °C with a 2 mol % catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol %) for the coupling of aryl chlorides with anilines (max TON: 19 600).     

Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals

Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS‐QB3 ab initio (AI) calculations by using conventional transition‐state theory within the high‐pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group‐additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α‐hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K. From a training set of 60 hydrogen abstractions from oxygenates by carbon‐centered radicals, 15 GA values (ΔGAV^os) are obtained for both the forward and reverse reactions. Among them, four ΔGAV^os refer to primary contributions, and the remaining 11 ΔGAV^os refer to secondary ones. The accuracy of the model is further improved by introducing seven corrections for cross‐resonance stabilization of the transition state from an additional set of 43 reactions. The determined ΔGAV^os are validated upon a test set of AI data for 17 reactions. The mean absolute deviation of the pre‐exponential factors (log A) and activation energies (E_a) for the forward reaction at 300 K are 0.238 log(m³ mol^?1 s^?1) and 1.5 kJ mol^?1, respectively, whereas the mean factor of deviation <ρ> between the GA‐predicted and the AI‐calculated rate coefficients is 1.6. In comparison with a compilation of 33 experimental rate coefficients, the <ρ> between the GA‐predicted values and these experimental values is only 2.2. Hence, the constructed GA model can be reliably used in the prediction of the kinetics of α‐hydrogen‐abstraction reactions between a broad range of oxygenates and oxygenate radicals.     

The rheological properties of hydrogenated castor oil crystals

The present study focuses on the rheological performance of a surfactant-rich aqueous suspension containing hydrogenated castor oil (HCO) crystals. HCO can be typically crystallized in five distinct shapes: spherically shaped, irregularly shaped, star-shaped (also called rosettes), short needles, and thick or thin fibers. The effect of the differences in shape on the rheological performance is studied, and the rheological properties are compared to the behavior of other triacylglycerol’s (TAG) suspensions. A suspension of TAG crystals usually behaves as a colloidal gel wherein a colloidal gel is defined as a network of flocs, with each floc being an aggregate of smaller subunits. All of these surfactant-rich aqueous suspensions of HCO crystals behaved according to a colloidal gel in the transient regime, independent of the studied crystal shapes, except the long thin fibers at a concentration above 0.1 wt% HCO transitioning from a heterogeneous fractal rod network to a homogeneous rod network, shifting from a colloidal gel to a glass.     

3‐O‐Sulfation of Heparan Sulfate Enhances Tau Interaction and Cellular Uptake

Prion‐like transcellular spreading of tau in Alzheimer's Disease (AD) is mediated by tau binding to cell surface heparan sulfate (HS). However, the structural determinants for tau–HS interaction are not well understood. Microarray and SPR assays of structurally defined HS oligosaccharides show that a rare 3‐O‐sulfation (3‐O‐S) of HS significantly enhances tau binding. In Hs3st1^?/? (HS 3‐O‐sulfotransferase‐1 knockout) cells, reduced 3‐O‐S levels of HS diminished both cell surface binding and internalization of tau. In a cell culture, the addition of a 3‐O‐S HS 12‐mer reduced both tau cell surface binding and cellular uptake. NMR titrations mapped 3‐O‐S binding sites to the microtubule binding repeat 2 (R2) and proline‐rich region 2 (PRR2) of tau. Tau is only the seventh protein currently known to recognize HS 3‐O‐sulfation. Our work demonstrates that this rare 3‐O‐sulfation enhances tau–HS binding and likely the transcellular spread of tau, providing a novel target for disease‐modifying treatment of AD and other tauopathies.     

Experimental and Computational Studies of Anti‐Bredt Amidinium Salts

Experimental and computational investigations of anti‐Bredt amidinium salts are presented. Calculations show that the pyramidalization of an amino group can significantly destabilize the formal carbocation center of amidiniums, due to the decreased π donation. In some cases, the unfavorable ‐I effect of nitrogen surpasses its beneficial +M effect, and amidiniums become less stable than iminiums. It is shown that although 1‐aza‐3‐azonia[3.3.1]bicyclo‐non‐2‐enes can be isolated, they feature a nonclassical reactivity, which is more typical for iminium than amidinium salts, such as pronounced electrophilicity and azomethineylide instead of carbene formation.