Regio- and Diastereoselective Hydrophosphination and Hydroamidation of gem-Difluorocyclopropenes.

In this study, concise, efficient, and modular hydrophosphinylation and hydroamidation of gem-difluorocyclopropenes were disclosed in a mild and transition-metal-free pattern. Through this approach, phosphorus, and nitrogen-containing gem-difluorocyclopropanes were produced in moderate to good yields with excellent regio- and diastereoselectivity. Readily available gem-difluorocyclopropenes and nucleophilic reagents, along with inexpensive inorganic bases, were employed. Multiple synthetic applications, including gram-scale and derivatization reactions and modification of bioactive molecules, were subsequently elaborated.

Cobalt-catalyzed enantioselective C-H/N-H annulation of aryl sulfonamides with allenes or alkynes: facile access to C-N axially chiral sultams.

Herein we report a cobalt-catalyzed enantioselective C-H/N-H annulation of aryl sulfonamides with allenes and alkynes, using either chemical or electrochemical oxidation. By using O2 as the oxidant, the annulation with allenes proceeds efficiently with a low catalyst/ligand loading of 5 mol% and tolerates a wide range of allenes, including 2,3-butadienoate, allenylphosphonate, and phenylallene, resulting in C-N axially chiral sultams with high enantio-, regio-, and position selectivities. The annulation with alkynes also exhibits excellent enantiocontrol (up to >99% ee) with a variety of functional aryl sulfonamides, and internal and terminal alkynes. Furthermore, electrochemical oxidative C-H/N-H annulation with alkynes is achieved in a simple undivided cell, demonstrating the versatility and robustness of the cobalt/Salox system. The gram-scale synthesis and asymmetric catalysis further highlight the practical utility of this method.

Molecular dynamics simulations of the initial oxidation process on ferritic Fe-Cr alloy surfaces.

Oxidation processes of metallic interconnects are crucial to the operation of solid oxide fuel cells (SOFCs), and ferritic Fe-Cr alloy is one of the most important metallic interconnect materials. Based on the ReaxFF reactive potential, the interaction of O2 molecules with three types of surfaces (100, 110, 111) of ferritic Fe-Cr alloy has been studied by classical molecular dynamics at constant O2 concentrations and temperatures. The initial oxidation process is systematically studied according to the analysis of O2 absorption rate, charge variations, charge distributions, mean squared distributions, and oxidation rate. The results reveal that it is easier and faster for the Cr atoms to lose electrons than for the Fe atoms during the oxidation process. The obtained oxidation rate of Cr atoms is larger and the formation of Cr2O3 takes precedence over that of FeO. And the thickness of oxidation layers of different surfaces could be determined quantitatively. We also find that the high O2 concentration accelerates the oxidation process and obviously increases the thickness of oxidation layers, while the temperature has a weaker effect on the oxidation process than the O2 concentration. Moreover, the (110) surface presents the best oxidation resistance compared to the other two surfaces. And the (110) surface is efficient in preventing Fe atoms from being oxidized. Here we explore the initial oxidation process of Fe-Cr alloy and the corresponding results could provide theoretical guides to the related experiments and applications as metallic interconnects.

Geochemistry and tectonic significance of late Paleoproterozoic A-type granites along the southern margin of the North China Craton.

The Longwangzhuang pluton is a typical example of Paleoproterozoic A-type granite intrusions at the southern margin of the North China Craton. This pluton is composed of arfvedsonite granite and minor aegirine-augite granites. Samples from both granite types display similar zircon U-Pb ages with 207U-206Pb ages of 1612 ± 19 Ma [mean square weighted deviation (MSWD) = 0.66] and 1609 ± 24 Ma (MSWD = 0.5), respectively. The granites exhibit similar high silica (SiO2 = 71.1-73.4 wt.%), high alkaline (Na2O + K2O = 8.10-9.26 wt.%, K2O/Na2O > 1), and low Al2O3 (11.8-12.8 wt. %) contents and metaluminous to weakly peraluminous bulk chemistry. The chemical variations of the Longwangzhuang pluton suggest the effects of mineral fractionation. In addition, all samples show typical characteristics of A-type granites, such as high 10000Ga/Al ratios (4.10-7.28), high FeOtot/(FeOtot + MgO) ratios (0.88-0.99), and high Zr (484-1082 ppm), Ce (201-560 ppm), and Y (78-156 ppm) contents. The εNd(t) values and the (206Pb/204Pb)t, (207Pb/204Pb)t, and (208Pb/204Pb)t ratios of the arfvedsonite granite samples vary from -4.6 to -5.3, 15.021 to 17.349, 15.241 to 15.472, and 33.206 to 36.905, respectively, and those for the aegirine-augite granite sample amount at -0.2, 14.421, 15.175, and 33.706. The distinct and variable Nd and Pb isotope values indicate the presence of heterogeneous protoliths. Based on its geochemistry, its low initial Pb isotope ratios, and its enrichment in Nd isotopes, we infer that the Longwangzhuang A-type granite is the partial melting product of basement rocks such as the Taihua Group gneisses accompanied by some involvement of juvenile material from the mantle. Together with published data from other Paleoproterozoic A-type granite plutons exposed at the southern margin of the craton, our findings suggest that these granites had a similar origin. Furthermore, geochemically, they can be divided into two groups: A2-type, which formed earlier (~1.8-1.6 Ga), and A1-type, which formed later (~1.6-1.5 Ga). Combining this information with the variations in whole-rock Nd and zircon Hf isotopic composition at ca. 1.6 Ga, we propose that tectonic transformation from post-orogenic to anorogenic magmatism occurred at the southern margin of the North China Craton at that time.