(Me3Si)2NBCl2和(Me3Si)2NB(Cl)NHSiMe3的合成及其成环反应

自从氮化硼陶瓷纤维用聚合物先驱体法[1]合成以后,硼氮六元环化合物越来越为人们所重视[2],文中在制备氮化硼纤维先驱体的过程中,合成了其中间产物,通过热缩合成环反应,合成了含有硼氮六员环的化合物,并采用色-质联用技术对其进行了表征。1　实验部分参照文献[3],改用液氮和丙酮为冷冻剂,控制温度在-50到-40℃,搅拌下向三氯化硼的正戊烷溶液中缓慢滴加三乙胺的正戊烷溶液,滴完后Ｎ2气氛下-50℃加丙酮冷凝回流2ｈ,慢慢由-50℃升至室温,抽滤即得到白色产物Ｅｔ3ＮＢＣｌ3(Ａ)。将Ａ溶于适量苯中[4,5],加入等物质的量的三乙胺,加热回流搅拌…     

Borazine as a sensor for fluoride ion: a computational and experimental study

The computational and experimental studies have revealed that even simple molecule like borazine can act as a sensor for fluoride ions. This study further reported the various binding modes of analytes using quantum chemical calculations and the nature of such interactions have been examined using electron density surface analysis. Total charge transfer analysis (q_CT) correlates well with the binding affinities of analytes with the borazine receptor.     

六元环硼氮烷对称取代方酸的电子光谱和非线性光学性质的DFT研究

用量子化学密度泛函理论B3LYP方法,在6-31G(d)水平上对环硼氮烷和苯基对称取代方酸进行几何构型优化.以此为基础,利用TD-DFT方法得到方酸衍生物的UV-Vis吸收光谱.进一步引入外电场,用有限场(FF/DFT-B3LYP)方法探讨了各体系的三阶非线性光学性质(NLO).计算结果显示,对称环硼氮烷取代的方酸衍生物性质不同于苯环取代,取代位置对电荷分布、分子轨道特征和非线性光学性质的影响很大.氮原子与方酸相连时对提高方酸体系的三阶非线性光学性质十分有效,其NLO系数可达2.3808×10^-24C·m.     

Synthesis and characterization of trimetallic complexes with a borazine core

Treatment of [Cp*Ru(dppe)]⁺ with B-triethynyl-N-trimethylborazine and piperidine produces the trimetallic complex [Cp*Ru(dppe)(CC)]₃B₃N₃Me₃, the structure of which has been confirmed by X-ray diffraction. Reaction of RuHCl(CO)(PPh₃)₃ with B-triethynyl-N-trimethylborazine produces the trimetallic complex [RuCl(CO)(PPh₃)₂(CH=CH)]₃B₃N₃Me₃.     

High Resolution FTIR Spectroscopy of Borazine: The Parallel Bands ν8 and ν9 of 10B314N31H6

The high resolution (0.002 cm^–1) FTIR spectra of the A ‐fundamental bands ν₈ and ν₉ of ¹⁰B₃¹⁴N₃¹H₆ were investigated for the first time. Both fundamental bands show a typical parallel band structure, thus confirming the D_3h symmetry of the molecule under consideration. Whilst ν₉ is unperturbed at the present level of precision, ν₈ is heavily perturbed, probably by an α^BB‐resonance with the IR‐forbidden combination tone ν₁₀ + ν₁₇. The molecular constants of the ground state and of the states v₈ = 1 and v₉ = 1, respectively, are given.     

π-Molecular complexes: A modified CNDO study of the benzene-borazine system

The standard CNDO/2 method is shown to be unable to produce meaningful potential curves for π-π-type molecular complexes. A modification of this method in which pairs of atoms associated with the same molecule and with different molecules are differentiated leads to reduced intermolecular bonding and provides reasonable stabilization energies and intermolecular separations. Calculations based on this modified method indicate that benzene-borazine and borazine-borazine complexes in which the molecules are symmetrically disposed in parallel planes can exist in the ground state. The stabilization energies are calculated to be in the range 2–5 kcal/mole for benzene-borazine and 5–18 kcal/mole for borazine-borazine, with interplanar separations near 3 Å in both cases.     

Preparation and characterization of boron nitride coatings on carbon fibers from borazine by chemical vapor deposition

Boron nitride (BN) coatings were deposited on carbon fibers by chemical vapor deposition (CVD) using borazine as single source precursor. The deposited coatings were characterized by scanning electron microscopy (SEM), Auger electron spectroscopy (AES), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The effect of temperatures on growth kinetics, morphology, composition and structure of the coatings was investigated. In the low temperature range of 900 °C-1000 °C, the growth rate increased with increasing temperature complying with Arrhenius law, and an apparent active energy of 72 kJ/mol was calculated. The coating surface was smooth and compact, and the coatings uniformly deposited on individual fibers of carbon fiber bundles. The growth was controlled by surface reaction. At 1000 °C, the deposition rate reached a maximum (2.5 μm/h). At the same time, the limiting step of the growth translated to be mass-transportation. Above 1100 °C, the growth rate decreased drastically due to the occurrence of gas-phase nucleation. Moreover, the coating surface became loose and rough. Composition and structure examinations revealed that stoichiometric BN coatings with turbostratic structure were obtained below 1000 °C, while hexagonal BN coatings were deposited above 1100 °C. A penetration of carbon element from the fibers to the coatings was observed.     

Olefin hydroboration of borazine with vinylsilanes as precursors of Si-B-C-N ceramics

A processible polymeric precursor for Si-B-C-N ceramics was prepared by a hydroboration reaction between borazine and dimethyldivinylsilane using no catalyst with a synthetic yield 85%. The synthesized liquid polymer with an approximately 40% ceramic yield changed to an insoluble solid via a cross-linking reaction of the unreacted vinyl groups to the B-C alkyl bridges between the borazine ring and silane as post-heated from 200 to 600 °C. The insoluble solid was then transformed to SiCN and BN amorphous structures when pyrolyzed to 1400 °C. The synthetic and ceramic conversion chemistry was thoroughly investigated by infrared, ¹H, ¹¹B, ¹³C and ²⁹Si nuclear magnetic resonance spectroscopy, X-ray diffraction and thermal gravimetric analysis.     

Electron-beam assisted growth of hexagonal boron-nitride layer

It has been known that a good quality h-BN layer can only be grown within a narrow temperature window of 1020–1100 K on a copper substrate. We found that the growth temperature window on Cu(111) surface could be lowered up to 100 K by ionizing and/or exciting borazine precursor gas with an electron-beam. The structures of a hexagonal boron nitride (h-BN) layers grown at various substrate temperatures on a Cu(111) were examined using scanning tunneling microscopy. We found that the grown h-BN film exhibits highly inert behavior with wide bandgap semiconductor characteristics.     

Synthesis of B-trisubstituted borazines via the rhodium-catalyzed hydroboration of alkenes with N,N′,N″-trimethyl or N,N′,N″-triethylborazine

Hydroboration of terminal and internal alkenes with N,N′,N″-trimethyl- and N,N′,N″-triethylborazine was carried out at 50 °C in the presence of a rhodium(I) catalyst. Addition of dppb or DPEphos (1 equiv.) to RhH(CO)(PPh₃)₃ gave the best catalyst for hydroboration of ethylene at 50 °C, resulting in a quantitative yield of B,B′,B″-triethyl-N,N′,N″-trimethylborazine. On the other hand, a complex prepared from (t-Bu)₃P (4 equiv.) and [Rh(coe)₂Cl]₂ gave the best yield for hydroboration of terminal or internal alkenes.