含硼抗癌化合物的研究——Ⅲ含B-N内配键的螯合二芳基硼化合物的合成及其抗癌活性

含B-N内配键的螯合二芳基硼化合物可认为是一类结构新型的化学抗癌剂。本文利用二芳基硼酸丁酯与氨基乙醇或α-氨基酸作用合成了15个这类新化合物,并进行了抗癌试验。初步药效表明,化合物3、4、8、9、11、12、13、14、15对小白鼠S_(180)有32～71％的抗癌活性。     

改进硼化合物焰色反应的实验研究

研究了分别利用蒸发皿和粉笔进行硼化合物焰色反应的实验效果,重点研究了以粉笔作载体时,硼化合物用量、乙醇纯度和用量、浓硫酸用量等因素对硼化合物焰色反应的火焰高度、燃烧时间等的影响,并得出最佳实验条件。     

芳烃与烷烃化合物参与的光化学与电化学硼化反应

有机硼化合物是重要的有机合成砌块,并被广泛应用于材料与医药领域.发展实用、简洁的硼化反应合成有机硼化合物一直是有机硼化学的核心课题之一.近年来,光化学和电化学硼化反应取得了快速发展,已成为合成有机硼化合物的重要方法.从能量来源及反应底物类型的角度出发,总结了芳烃与烷烃化合物参与的光化学、电化学和光电化学硼化反应的研究进展,同时也对今后光化学与电化学硼化反应的发展方向进行了展望.     

超价化合物的结构特征和反应活性

超价分子和离子是一类奇特而迷人的物种,它们的出现对经典的Ｌｅｗｉｓ－Ｌａｎｇｍｕｉｒ主族元素价民键理论提出了挑战。本文重点阐述了超价化合物的结构特征和反应活性。     

有机硼化合物的分类和名称

按照狭义的分类方法,对含有硼碳键的有机硼化合物的分类进行探讨。根据结构类型,有机硼化合物可以分为烃基硼烷、烃基硼酸(酯)、烃基硼烷路易斯碱加合物和离子型有机硼化合物、有机硼杂环及其金属配合物、碳硼烷簇合物及其金属化合物等类型。对不同类型的有机硼化合物的命名进行了归纳,并给出了一些代表性化合物的英汉对照名称。     

芳基多硼化合物的制备及其选择性偶联反应

正Angew.Chem.Int.Ed.2014,53,1822~1826钯催化有机硼酸与卤化物的反应,即Suzuki-Miyaura交叉偶联反应是应用最广泛的C—C键形成方法之一.为了更有效地合成更复杂的化合物,多官能团底物的制备和选择性反应就显得非常重要.多卤化物的研究已经广为人知,而反应性可以区分的多硼化合物则更具有挑战性,仅在近年来引起合成化学家的关注.文献中一些双硼化合物都是从含有其它官能团的有机硼制得,因而制备步骤繁琐,限制了其应用范围.西安交通大学前沿科学技术研究院有机     

四种硝基苯的电化学行为及其反应活性的理论计算

在滴汞电极上研究了硝基苯、对硝基甲苯、间二硝基苯及2，4-二硝基氯苯的电化学行为，并用量子理论对四种硝基苯化合物的反应活性进行了预测，理论与试验结果基本一致，据此提出了预测分子的电化学活性的方法。     

联萘双金属化合物对胺基氯硼烷类的单转烃化反应及2-联萘基硼化合物的合成

一类新反应现象被描述。2.2′-二锂联萘或2.2′-双格氏化联萘当与Et_2NBCl_2及Et_2NB(Ph)Cl反应时,仅以一个M—C键参与亲核烃化,另一M—C键因可能的七员环过渡态而失活。反应分别给出仅在联萘2-位取代的硼化合物Ⅲ或Ⅳ,而得不到2,2′-双位取代的硼化合物Ⅰ或Ⅲ。五个新硼化合物被合成,并讨论了反应机理。     

硼的化合物就是缺电子化合物吗

位于周期表第二周期、第三主族的硼元素是缺电子元素。硼元素主要形成共价型缺电子化合物。硼烷、卤化硼、硼酸是常见的硼的化合物。通过讨论这些硼化合物的结构,指出缺电子化合物能够稳定存在的原因。介绍了三氧化二硼的3种存在形式以及α-B2O3的晶体结构。     

封闭型硼烷B15H15^2—（D3h）的结构及稳定性的从头算分析

利用量子化学从头算方法在ＨＦ／６－３１Ｇ水平上，优化计算了带２个负电荷的封闭型硼烷Ｂ１５Ｈ１５＾２－（Ｄ３ｈ）的结构、能量和正则振动频率。该硼烷的简正振动频率计算表明，它是ＨＦ／６－３１Ｇ势能超曲面上的真实稳定点。理论预测它在化学上和动力学上都是稳定的。     

A Surprising Adduct of a closo Cluster

The geometry of the Si ₂ B ₁₀ framework remains nearly unchanged when the Si–Si edge is bridged by an electron-donating amido group. This finding is clearly evident from the single-crystal X-ray structure analysis and ab initio calculations of the uprecedented adduct that is formed by the addition of Et₂N⁻ to o-silaborane (structure depicted bottom right).     

A Five-Membered Ring with Three Negative Charges and Solvent-Free Lithium Counterions

Remarkably short distances to the ring plane are shown by the η⁵-bound lithium ions in the first compound with a triply negatively charged five-membered ring, 1 , which was obtained by reduction of 2 with lithium. R=CH(SiMe₃)₂, Dur=2,3,5,6-tetramethylphenyl.     

Theoretical modeling of infrared spectra of benzoic acid and its deuterated derivative

Theoretical simulation of the ν_s stretching band is presented for benzoic acid and its OD derivative at 300 K. The simulation takes into account an adiabatic coupling between the high-frequency O–H(D) stretching and the low-frequency intermolecular OO stretching modes, linear and quadratic distortions of the potential energy for the low-frequency vibrations in the excited state of the O–H(D) stretching vibration, resonance interaction between the two hydrogen bonds in the dimer, and Fermi resonance between the fundamental ν OH(D) stretching and the overtone of the δ O–H(D) bending vibrations.

Infrared, far-infarared, Raman and low-frequency Raman spectra of the polycrystalline benzoic acid and its deuterated form have been measured. The geometry and experimental frequencies are compared with the results of our B3LYP/6-311++G** and B3LYP/cc-pVTZ calculations.     

桥联双（甲巯咪唑）化合物的合成和配位性能

研究了桥联双(甲巯咪唑)化合物(Ⅰ_a—Ⅳ_a、Ⅰ_b)的合成和配位性能。UV谱显示Ⅰ_a—Ⅳ_a与UO_2~(2+)离子(硬酸)配位,溶液中形成3:1的配合物。Ⅰ_b与Hg~(2+)、Au~(3+)离子(软酸)配位形成2:1的配合物,用CNDO/2方法计算了各配体分子中原子净电荷密度和HOMO、LUMO能量。     

Homoleptic Lanthanide Complexes of Chelating Phosphanamides—An Experimental and Theoretical Study

Four chelating ligands are present in the first phosphanamide complexes of Group 3 metals and the lanthanides (see structure shown). However, these ligands coordinate to form a distorted molecular structure. The compounds were characterized by single-crystal X-ray structure analysis and quantum-mechanical investigations with density functional theory and MP2 methods.     

The Parent Hexacarbaborane arachno-C6B6H12 and a Methylated Pentacarbaborane arachno-CH3C5B7H12: Domains of Incipient Hydrocarbon Behavior within Borane Clusters

Increasingly pronounced hydrocarbon character is exhibited by C₆H₆B₁₂, the first unsubstituted hexacarbaborane, and CH₃C₅B₇H₁₂, the first cluster pentacarbaborane. These compounds shed light on the structural dichotomy between open hydrocarbon skeletons and polyhedral borane frameworks for high-carbon carboranes.     

金属硼化物结构与稳定性的理论研究

用ＨＦ／３－２１Ｇａｂｉｎｉｔｉｏ法对金属硼化物ＭＢ２／ＭＢ２（Ｍ＝Ｌｉ，Ｎａ，Ｂｅ，Ｍｇ，Ａｌ）的７５个电子态结构进行能量梯度法优化，再用大基组二次且上互作用ＱＣＩＳＤ（Ｔ）／６－３１１Ｇ进行单点计算，得到了结构参数总能量，为了考察各原子簇的稳定性，还对２４个碎片的７０多个电子态，求得相应的ＱＣＩＳＤ（Ｔ）能量，在此基础上计算了原子化能、电离能、离解通道和碎片化能，得到了原子簇的稳定性规律。     

Simulation of the Solid State Vibrational Spectra of Aminodichloroborane and Ammonia Boron Trichloride

This is the second part of a quantum chemical investigation on the reaction between boron trichloride and ammonia. In part I [9] we focused on the energetic course of successive chlorine substitutions which are relevant for the chemical vapor deposition of BN. In this work we analyze in detail the vibrational spectra of reaction products accessible at room temperature. Regarding an experimental IR spectrum of the condensation product of the reaction between BCl₃ and NH₃ [10], there are more signals than expected for monomeric aminodichloroborane. Since this molecule shows the tendency to oligomerize, we have studied whether the presence of aminodichloroborane dimers or trimers or an impurity of the ammonia boron trichloride complex – an intermediate from which aminodichloroborane is formed – can explain the shape of the measured spectrum. To this end we have calculated the vibrational frequencies of monomeric, dimeric, and trimeric BCl₂NH₂, H₃N · BCl₃, and several van der Waals complexes at the level of a Møller‐Plesset second order perturbation theory. For the verification of the methodology, the vibrational frequencies of the dimethylaminodichloroborane molecule have been determined, in good accord with experimental gas phase spectra. Also the solid state spectrum of H₃N · BCl₃ is well reproduced by the computed vibrational spectrum of the monomeric adduct and a hydrogen‐bonded aggregate. Our studies concerning the spectrum of the condensation product of the reaction of boron trichloride with ammonia indicate that the substance investigated by Kwon and McGee had contained, besides monomeric aminodichloroborane, also its trimer and ammonia boron trichloride.     

Theoretical Design of Strong Neutral Radical–Boron Adducts: Trisubstituted Boranes as Potential Radical Scavengers

The conditions of formation of strong two‐center one‐electron bonds in neutral compounds are discussed. Both molecular orbital and valence bond analyses show that good candidates are adducts of radicals ^.AR₃ (A=C, Si, Ge) of low ionization energy (IE) with boranes BX₃ of high electron affinity (EA). This is confirmed by ab initio calculations. The bond energy of adducts of B(CF₃)₃ with various radicals ranges from 18 kcal mol^?1 for ^.CH₃ to approximately 40 kcal mol^?1 for Me₃Si^., and a clear correlation with IE–EA difference is found. This allows one to expect B(CF₃)₃, among other fluoroboranes, to be an efficient radical scavenger.