Theoretical investigations on thermal rearrangement reactions of (aminomethyl)silane

Thermal rearrangement reactions of (aminomethyl)silane H(3)SiCH(2)NH(2) were studied by ab initio calculations at the G3 level. The results show that two dyotropic reactions could happen when H(3)SiCH(2)NH(2) is heated. In one reaction, the silyl group migrates from the carbon to the nitrogen atom while a hydrogen atom shifts from the nitrogen to the carbon atom, forming (methylamino)silane CH(3)NHSiH(3) (reaction A). This reaction can proceed via three paths: a path involving two consecutive steps with two transition states and one intermediate metastable carbene species (A-1); and two concerted paths (A-2 and A-3). In the other reaction, the amino group migrates from the carbon to the silicon atom while a hydrogen atom shifts from the silicon to the carbon atom, via a double three-membered ring transition state, forming aminomethylsilane CH(3)SiH(2)NH(2) (reaction B). Reaction rate constants, changes (DeltaS(#), DeltaH, and DeltaG) in thermodynamic functions and equilibrium constants of the reactions were calculated with the MP2(full)/6-311G(d,p) optimized geometries, harmonic vibrational frequencies and G3 energies of reactants, transition states, intermediates and products with statistical mechanical methods and the conventional transition-state theory (TST) with Wigner tunneling approximation over a temperature range 400-1800 K.     

Direct synthesis of hyperbranched ethene oligomers and ethene-MA co-oligomers using iminopyridyl systems with weak neighboring group interactions

The synthesis of hyper-branched ethene oligomers through catalytic insertion reactions with late transition metal catalysts is unique in its synthetic and practical scope. In this study, a series of iminopyridyl Ni(II) and Pd(II) complexes with electron-rich distal aryl motifs were synthesized and characterized. These complexes were very efficient in ethene oligomerization and co-oligomerization with methyl acrylate (MA). Hyperbranched ethene oligomers with different microstructures were generated using different metal species in ethene oligomerization. More importantly, hyperbranched ethene-MA co-oligomers with varying incorporation ratios were generated via ethene and MA co-oligomerization using the Pd(II) complexes. Most notably, weak neighboring group interactions of distal aryl motifs in the nickel system are more effective in influencing the microstructure of ethene oligomers than the corresponding palladium system.     

Direct Synthesis of Functionalized High‐Molecular‐Weight Polyethylene by Copolymerization of Ethylene with Polar Monomers

The introduction of even a small amount of polar functional groups into polyolefins could excise great control over important material properties. As the most direct and economic strategy, the transition‐metal‐catalyzed copolymerization of olefins with polar, functionalized monomers represents one of the biggest challenges in this field. The presence of polar monomers usually dramatically reduces the catalytic activity and copolymer molecular weight (to the level of thousands or even hundreds Da), rendering the copolymerization process and the copolymer materials far from ideal for industrial applications. In this contribution, we demonstrate that these obstacles can be addressed through rational catalyst design. Copolymers with highly linear microstructures, high melting temperatures, and very high molecular weights (close to or above 1 000 000 Da) were generated. The direct synthesis of polar functionalized high‐molecular‐weight polyethylene was thus achieved.     

Theoretical studies on the structures and isomerization of the LiSiF3 system

Various possible isomers of LiSiF₃ system and isomerization between them have been studied at G2(MP2) level usingab initio calculations. The relative energies of four minimum points on the potential energy surface are-128.6,-194.3,-12.7 and-122.8 kJ/mol (taking the sum of the energies of LiF and SiF₂ as zero). The structural energy of the four-membered ring that contains three F-Si-F-Li four-membered rings with C_3v symmetry is the lowest. The highest potential barrier for the isomerization of the remaining three- or four-membered structure is 12.5 kJ/ mol. Project supported by the National Natural Science Foundation of China (Grant No. 29673026).     

Experimental study of large-amplitude standing-wave field obtained in a standing-wave tube with uniform cross section

A large-amplitude standing-wave field of 182.1 dB is obtained under the excitation at the resonant frequency of the lst-order peak of the sound pressure transfer function in an improved standing-wave tube experimental system,and saturation of harmonics and waveform distortion are investigated experimentally for the large-amplitude standing-wave fields obtained under the excitations at the resonant frequencies of the 1 st-to the 5 th-order peaks.The results show that although the sound pressure level has reached 182.1 dB under the excitation at the resonant frequency of the 1 st-order peak,the waveform distortion is the minimum and the harmonic saturation is not observed.However,the large-amplitude standing-wave field excited at the resonant frequency of the 3 rd-order peak exhibits the trend of the harmonic saturation.Comparison of the large-amplitude standing-wave fields obtained under the excitations at valley resonant frequencies shows that the standing-wave field excited at the resonant frequency of the 1 st-order valley has the largest SPL,but also has the largest waveform distortion.Under the same source-driving voltage,the standing-wave field excited at the resonant frequency of the 1 st-order peak always has greater SPL than the standing-wave field excited at the resonant frequency of the 1 st-order valley.Hence,to obtain a large-amplitude standing-wave field,it's better to excite at the resonant frequency of the 1 st-order peak of the SPTF by using loudspeaker in a standing-wave tube with uniform cross section.     

Theoretical study on the isomeric structures and the stability of silylenoid (Tsi)Cl2SiLi (Tsi = C(SiMe3)3)

The structures and isomerization of silylenoid (Tsi)Cl(2)SiLi (Tsi = C(SiMe(3))(3)) were studied by density functional theory (DFT) at the B3LYP/6-31G(d) level. Four equilibrium structures and three isomeric transition states were located. The three-membered ring and p-complex structures, 1 and 2, are the two most stable forms. Two other local minima, the sigma-complex 3 and tetrahedron structure 4, should rearrange to 1 with very low barriers, and then to the most stable isomer 2. To exploit further the stability of silylenoid (Tsi)Cl(2)SiLi, the insertion reactions of 2 and silylene (Tsi)ClSi into the HF molecule have been investigated at the B3LYP/6-31G(d) level, respectively. The results show that the insertion of 2 into HF is very similar to that of (Tsi)ClSi into HF, but the latter is more favorable. To probe the influence of the substituent Tsi on the stability of silylenoid (Tsi)Cl(2)SiLi, the isomers and insertion reaction of silylenoid CH(3)Cl(2)SiLi were investigated in a similar way of those with (Tsi)Cl(2)SiLi. The results indicate that silylenoid containing very bulky group Tsi exhibits unusual stability because of the severe steric hindrance produced by Tsi at the center to which it is attached.     

Blind quantum computation with identity authentication

Blind quantum computation (BQC) allows a client with relatively few quantum resources or poor quantum technologies to delegate his computational problem to a quantum server such that the client's input, output, and algorithm are kept private. However, all existing BQC protocols focus on correctness verification of quantum computation but neglect authentication of participants' identity which probably leads to man-in-the-middle attacks or denial-of-service attacks. In this work, we use quantum identification to overcome such two kinds of attack for BQC, which will be called QI-BQC. We propose two QI-BQC protocols based on a typical single-server BQC protocol and a double-server BQC protocol. The two protocols can ensure both data integrity and mutual identification between participants with the help of a third trusted party (TTP). In addition, an unjammable public channel between a client and a server which is indispensable in previous BQC protocols is unnecessary, although it is required between TTP and each participant at some instant. Furthermore, the method to achieve identity verification in the presented protocols is general and it can be applied to other similar BQC protocols.     

Ab initio study of the complexes of first-row transition-metal ions with CH, CH2, and CH3

The geometries and bonding characteristics of the complexes of the first-row transition-metal ions with CH, CH₂ and CH₃ were investigated byab initio molecular orbital theory. MCH⁺ and MCH₂ ⁺ are linear and coplanar, respectively. Both of them are with obvious treble or double bond characteristics, but these multiple bonds are mostly “imperfect”. The calculated bond dissociation energies of , and are mostly close to the experimental values, and appear in similar periodic trends from Sc to Zn. Project supported by the National Natural Science Foundation of China (Grant No. 29170070).     

含环氧基聚二甲基硅氧烷及其硫化过程的分子运动

采用扭辩分析法详细研究了含环氧基聚二甲基硅氧烷在１１０－２３０Ｋ范围内的的分子运动情况，讨论了氧基团对聚二甲基硅氧烷主链的玻璃化转变温度，次级转变温度、烷融温度及粘流浊国度等动态力学性能的影响。     

Facile and Efficient Synthesis of Carbosiloxane Dendrimers via Orthogonal Click Chemistry Between Thiol and Ene

A combination of a thiol‐Michael addition reaction and a free radical mediated thiol–ene reaction is employed as a facile and efficient approach to carbosiloxane dendrimer synthesis. For the first time, carbosiloxane dendrimers are constructed rapidly by an orthogonal click strategy without protection/deprotection procedures. The chemoselectivity of these two thiol–ene click reactions leads to a design of a new monomer containing both electron‐deficient carbon–carbon double bonds and unconjugated carbon–carbon double bonds. Siloxane bonds are introduced as the linker between these two kinds of carbon–carbon double bonds. Starting from a bifunctional thiol core, the dendrimers are constructed by iterative thiol–ene click reactions under different but both mild reaction conditions. After simple purification steps the fifth dendrimer with 54 peripheral functional groups is obtained with an excellent overall yield in a single day. Furthermore, a strong blue glow is observed when the dendrimer is excited by a UV lamp.