N-Aryloxide-Amidinate Thorium Complexes.

An N-aryloxide-amidine ligand (1), [ONNO] ligand, integrating phenoxide (PhO-) and amidine ligands through methylene linkers, was employed in actinide chemistry. Upon reaction of the deprotonated ligand with ThCl4(DME)2 in ether, the corresponding dimer complex 2 was obtained. Upon treatment of 2 with KCp* (Cp* = Cp(Me)5) in tetrahydrofuran, the corresponding {[ONNO]ThIVCp*(LiCl)}2 (4) was obtained. In complex 2, the two ArO- arms bonded from the same ligand to different ThIV centers. In contrast, both ArO- arms coordinated to the same metal center in 4. Notably, when a mixture of 2 and bipyridine was treated with one or two equiv of KC8, the [ONNO]ThIV-bipyridyl•̅ radical dimer complex (5) and [ONNO]ThIV-bipyridyl2- dianionic dimer species (6) were obtained, respectively.

Photochemical Benzylation of White Phosphorus.

Organophosphorus compounds (OPCs) have wide application in organic synthesis, material sciences, and drug discovery. Generally, the vast majority of phosphorus atoms in OPCs are derived from white phosphorus (P4). However, the large-scale preparation of OPCs mainly proceeds through the multistep and environmentally toxic chlorine route from P4. Herein, we report the direct benzylation of P4 promoted by visible light. The cheap and readily available benzyl bromide was used as a benzylation reagent, and tetrabenzylphosphonium bromide was directly synthesized from P4. In addition, the metallaphotoredox catalysis strategy was applied to functionalize P4 for the first time, which significantly improved the application range of the substituted benzyl bromide.

Study on the process of mass transfer and deterioration of limestone under dynamic dissolution of CO2 solution.

The long-term erosion of rock by solution can induce a series of karst problems. Therefore, this study focused on limestone and conducted dynamic dissolution experiments under deionized water and CO2 solution conditions to study the deterioration mechanism of limestone under nonequilibrium conditions. The results showed that the degree of degradation of the mechanical properties of the samples in a CO2 solution was obviously greater. In a deionized water environment, the degradation of the mechanical properties of the sample is mainly controlled by the physical softening action of the solution. In the CO2 solution environment, the degradation process can be divided into two stages. In the early stage of the experiment (10 days to 20 days), the degradation of mechanical properties of the sample is also controlled by the physical softening action of the solution. With increasing soaking time, the main rock-forming minerals of limestone gradually react with the CO2 solution, the degradation of the sample is controlled mainly by the chemical corrosion of the CO2 solution, and its degradation rate is much greater than that of physical softening. The results can be used as a reference for assessing the long-term stability of underground engineering in limestone karst development areas.

N-aryloxide-amidinate group 4 metal complexes.

A N-aryloxide-amidine ligand (H3L), integrating phenoxide (PhO-) and amidine ligands through methylene linkers, has been synthesized from 2-(aminomethyl)-6-(tert-butyl)phenol in two steps. Upon reacting the deprotonated H3L ligand with group 4 metal chloride MIVCl4, a corresponding (LMIV-Cl)2 dimer could be obtained. The coordination modes exhibit variation depending on the radius of the metal ions. In the case of (LTiIV-Cl)2, the two ArO- arms from the same ligand bond to two different Ti(IV) centers, while in the case of (LZrIV/HfIV-Cl)2, both ArO- arms coordinate with the same metal center. Moreover, the two C-N bonds in the amidinate moiety are localized in (LTiIV-Cl)2, whereas they delocalize in (LZrIV-Cl)2. Notably, (LHfIV-Cl)2 could further react with one equivalent of HfCl4, yielding the binuclear metal azide in the presence of KN3 and LiCl, where the coordination mode of the amidinate moiety changed from the bidentate chelating type to the bimetallic bridging coordination.

Study on the Corrosion Behavior of Cemented Organic Soil in Dianchi Lake, China.

To study the corrosion behavior of cement soil in peat soil, the experiment involves the preparation of peat soil by incorporating humic acid into cohesive soil with a lower organic matter content. Cement soil samples are then prepared by adding cement to the mixture. These samples are subjected to immersion in fulvic acid solution and deionized water to simulate different working environments of cement soil. The experiment considers immersion time as the variable factor. It conducts observations of apparent phenomena, ion leaching tests, and unconfined compression strength tests on the cement soil. The experiment results are as follows: (1) With increasing immersion time, the surface of the cement soil in the peat soil environment experiences the disappearance of Ca(OH)2 and calcium aluminate hydrate. Additionally, large amounts of bird dropping crystals precipitate on the surface and within the specimen. The cement soil undergoes localized disintegration due to extensive erosion caused by swelling forces. (2) In the peat soil environment, fulvic acid reacts with the hydration products of cement, resulting in partial leaching of ions such as Ca2+, Mg2+, Al3+, and Fe3+ into the immersion solution. The lower the pH of the fulvic acid immersion (indicating higher concentration), the more significant the ion leaching. Increasing the ratio of humic acid to cement can slow down the leaching of ions. The cement soil undergoes dissolutive erosion in the peat soil environment. (3) The peat soil environment exerts both strengthening and corrosive effects on the cement soil. Cement soil without humic acid exhibits noticeable corrosion in the peat soil environment, gradually decreasing strength as immersion time increases. The strength decreases by 83% from 28 to 365 days. In contrast, cement soil with humic acid experiences an initial period of strengthening, leading to a significant increase in strength in the short term (34% increase from 28 to 90 days). However, the corrosive effects gradually dominate, resulting in a decrease in strength over time. The strength decreases by 80% from 90 to 365 days. This study also explores the strengthening effects of peat soil on cement soil. It identifies phenomena such as extensive erosion and new substance precipitation in cement soil.