Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

Helicate tris(aryl)carbinolates bearing pendant NR2 donors – a new family of supporting ligands for the synthesis of Sc3+ alkyl complexes

The reactions of aryllithium reagents o-LiC₆H₄CH₂NR₂ with (MeO)₂CO afford two new tris(aryl)carbinols bearing pendant-NR₂ donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C₆H₄CH₂NMe₂)₃CO]Sc(CH₂SiMe₃)₂ featuring rigid binding of the alkoxy anion through a κ¹-O, κ²-N chelating coordination mode     

Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

First principles investigations of Fe,Co, Ni in model honeycomb carbon networks

The behaviors of ferromagnetic transition metals of the first period: Fe, Co and Ni are examined within density functional theory calculations in two dimensional carbon extended networks using model structure LiC₆. Around geometry optimized structures, the energy-volume equations of states considering non magnetic and spin polarized configurations established ferromagnetic ground states with magnetizations –reduced with respect to the metals’– of 2 μ_B for FeC₆ and 1 μ_B for CoC₆ while no magnetic solution could be identified for NiC₆. In the D_6h point group of the P6/mmm space group l_m decomposition of the d states results with increasing energy into doublet state E_1g with d(x²-y²) and d(xy); singlet state A_1g d(z²) and doublet state E_2g d(xz) and d(yz) lying on E_F and responsible of the onset of magnetic moments. This was mirrored via molecular orbital approach with a construct of Fe embedded between two extended carbon networks thus validating the model structure proposed for TC₆ compounds. The 100% polarization in one spin channel allows proposing potential uses in spintronics applications.     

Simultaneous Removal of Antibiotics and Heavy Metals with Poly(Aspartic Acid)-Based Fenton Micromotors

The discharge of diverse pollutants has led to a complex water environment and posed a huge health threat to humans and animals. Self-propelled micromotors have recently attracted considerable attention for efficient water remediation due to their strong localized mass transfer effect. However, a single functionalized component is difficult to tackle with multiple contaminants and requires to combine different decontamination effects together. Here, we introduced a multifunctional micromotor to implement the adsorption and degradation roles simultaneously by integrating the poly(aspartic acid) (PASP) adsorbent with a MnO₂-based catalyst. The as-prepared micromotors are well propelled in contaminated waters by MnO₂ catalyzing hydrogen peroxide. In addition, the catalytic ramsdellite MnO₂(R-MnO₂) inner layer is decorated with Fe₂O₃ nanoparticles to improve their catalytic performance, contributing to an excellent degradation ability with 90% tetracycline (TC) removal in 50 minutes by enhanced Fenton-like reactions. Combining the attractive adsorption capability of poly (aspartic acid) (PASP), the composite micromotors offer an efficient removal of heavy metal ions in short time. Moreover, the designed micromotors are able to simultaneously remove antibiotic and heavy metals in mixed contaminants circumstance just in single treatment. This multifunctional micromotor with distinctive decontamination ability exhibits a promising prospective in treating multiple pollutants in the future.     

Electroactive conducting polymers for corrosion control

There is an intensive effort underway to develop new corrosion control coatings for structural metals. In part, this effort has been motivated by the desire to replace chromium(VI)-containing coatings currently used for corrosion control of iron and aluminum alloys. Cr(VI) has been shown to be hazardous to the environmental and to human health, and its use in many countries will be sharply curtailed in the coming years. Electroactive conducting polymers (ECPs) represent a class of interesting materials currently being explored for use in corrosion control coating systems, possibly as a replacement for Cr(VI)-based coatings. The electroactivity and the electronic conductivity (or semiconductivity) of ECPs set them apart from traditional organic coatings. As with chromate, interesting and potentially beneficial interactions of ECPs with active metal alloys such as steel and aluminum are anticipated, with concomitant alteration of their corrosion behavior. A review of this active research area will be presented in two parts. Here in Part 1, a general introduction to the topic of corrosion control by ECPs will be presented, including an overview of corrosion and its control by traditional methods, an introduction to ECPs and their properties, and a discussion of the processing issues surrounding the use of ECPs as coatings. Part 1 also includes a review of the literature on the use of ECPs as coatings (or components of coatings) on non-ferrous active metals, principally aluminum and aluminum alloys, although some work on zinc, copper, silver, titanium and silicon will also be described. In Part 2 of this review (to be published in the next issue of this journal), the rather extensive literature on the use of ECPs for the corrosion control of ferrous alloys (steels) will be reviewed. Electronic Publication     

Finite-Band Potentials with Trigonal Curves

We construct Dubrovin equations and trace formulas for finite-band operators with trigonal curves and present some examples.     

Trace Functionals for a Class of Pseudo-Differential Operators in R n

In this paper we define trace functionals on the algebra of pseudo-differential operators with cone-shaped exits to infinity. Furthermore, we improve the Weyl formula on the asymptotic distribution of eigenvalues and make use of it in order to establish inclusion relations between the interpolation normed ideals of compact operators in L ²(R ⁿ ) and the above operator classes.     

CFD在燃煤细粒子凝聚过程中的应用

燃煤产生的细粒子富集了大量的有毒痕量元素,对大气环境和人类健康造成严重危害。本文针对燃煤细粒子的形成过程,在计算流体力学(CFD)的基础上,结合气溶胶动力学理论,模拟了烟气中细粒子在圆柱形流场中由于碰撞而凝聚的过程,并通过计算结果分析细粒子颗粒特征参量(速度、质量、直径和颗粒数目)随流场的变化趋势,为深入研究燃煤细粒子的形成演化机理提供理论基础。