Electronic structure and the hydrogen-shift isomerization of hydrogen nitryl HNO2

Summary Electronic structure of hydrogen nitryl HNO₂, a yet not identified entity, and the path of its possible isomerization totrans-HONO have been investigated byab initio SCF and MRD-CI computations using the 6-31G** basis set. HNO₂ isC _2v -symmetric and its ground state (¹ A ₁) is less stable thantrans-HONO by 66 kJ/mol (with the SCF vibrational zero-point energy correction). The lowest two excited singlet states (¹ A ₂ and¹ B ₁) are nearly degenerate, their vertical excitation energies being predicted to be 4.8 eV. The isomerization path is traced by the CASSCF procedure and the activation barrier height is evaluated by the CI treatment. HNO₂ in its ground state isomerizes totrans-HONO by maintaining the planar (C _s-symmetric) structure. The activation energy is calculated to be 171 kJ/mol, which is clearly lower than the calculated H-N bond energy (253 kJ/mol). The transition state seems to be more adequately described as an interacting system of proton and the nitrite anion rather than as a pair of two fragment radicals.     

FCC硫转移剂MgAlCuFe复合氧化物的结构与性能:金属盐前体的影响

分别以硝酸盐、盐酸盐和硫酸盐为金属盐前体,采用共沉淀法合成了MgAlCuFe类水滑石前驱体,经过700℃焙烧6h后,制得三种新型FCC硫转移剂.运用X射线衍射、热重、氮气吸附和红外光谱对这三种硫转移剂的结构和性能进行了表征,并采用改装的WRP-3热重天平评价了其氧化吸硫和还原脱硫的性能.结果表明,三种金属盐均可得到结构规整的类水滑石前驱体,经过焙烧后得到复合氧化物MgAlCuFe.与采用盐酸盐和硫酸盐作前体相比,由硝酸盐制得的硫转移剂具有较大的比表面积,其饱和吸附硫容和氧化吸硫速率均较高,6min可达到1.54g/g的饱和吸附能力,同时具有较强的还原脱硫能力.     

Synthesis and Crystal Structure of N-Phenylbis（ferrocenecarboxyl）imide

The ferrocenyl compound,N-phenylbis(ferrocenecarboxyl)imide (C28H23NO2Fe2,Mr=517.17),was synthesized and structurally characterized by means of X-ray single-crystal dif-fraction. It crystallizes in monoclinic,space group C2/c with a=21.374(14),b=10.430(7),c= 10.741(7) ,β=114.184(8)°,V=2184(2) 3,Z=4,Dc=1.573 g/cm3,F(000)=1064,μ(MoKα)= 1.355 mm–1,T=291(2) K,the final R=0.0548 and wR=0.1437 for 1524 observed reflections with I > 2σ(I). In this compound,the nitrogen atom links two ferrocenyl groups and one phenyl group forming a novel imido derivative.     

层状LiMnO_2的溶胶凝胶法合成及其改性

采用溶胶凝胶法合成了锂离子电池正极材料层状锰酸锂(o-L iMnO2),并对其进行了N i2+掺杂改性研究,优化了层状L iMnO2的合成路径及制备条件.采用XRD、充放电实验和交流阻抗测试方法研究了N i2+的掺入对o-L iMnO2充放电容量的影响.结果表明N i2+的掺入明显提高了锰酸锂的放电比容量和循环性能,抑制了循环过程中电池阻抗的增加.     

沐浴海绵Spongia zimocca aubspecles irregularia(Lendenfeld)中的含氮化合物

从沐浴海绵Spongia zimocca aubspecles irregularia(Lendenfeld)分离和处理得到3种含氮化合物,通过波谱法鉴定化学结构,化合物1为新的神经酰胺N-2-(1,3-二羟基-十五烷基)-2′,20′-二十一酰胺,2为神经酰胺(E)-N-2-(1,3-二羟基-4-十八烯基)-十六酰胺,3为醋酸胍.     

A Chiral Helical Compound Based on Achiral Components

The title compound, [Cu(dpa)(2,2'-bipy)(H2O)2]n 1 (H2dpa = diphenic acid and 2,2'- bipy = 2,2'-bipyridine), has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group P212121 with a = 10.597(4), b = 11.317(4), c = 17.630(7) , V = 2114.3(14) 3, C24H20CuN2O6, Mr = 495.97, Z = 4, Dc = 1.558 g/cm3, μ = 1.079 mm-1, F(000) = 1020, Flack value = 0.052(18), R = 0.0430 and wR = 0.1016 for 3381 observed reflections (I > 2σ(I)). In compound 1, the dpa ligands link metal ions into helical structures in the same direction.     

1－芳氧乙酰氧基－1－（1H－1，2，4－三唑－1－基）－3，3－二甲基－2－丁酮衍生物的研究

以三乙胺为缚酸剂，用芳氧乙酸同ω－溴代－ω－（１Ｈ－１，２，４－三唑－１－基）频哪酮反应，合成了一系列三唑类新化合物，探讨了化合物的合成方法。通过ＩＲ￣１ＨＮＭＲ、ＭＳ分析及元素分析确定了化合物的结构，生物活性测定结果表明，部分化合物具有良好的除草活性，同时表现出一定程度的植物生长调节活性及杀菌活性．     

2,8,9-三氧杂-5-氮杂-1-硼杂双环[3,3,3]十一碳烷的合成

本文报导了具有N→B配位键的2,8,9-三氧杂-5-氮杂-1-硼杂双环[3,3,3]十一碳烷的合成及性质。化合物(1)的制备已有报导,而化合物(2),(3)则为新的化合物。我们研究了它们的成环条件,制备的最佳条件及化学稳定性。     

一个二维梯状化合物[Ni(μ1，5-dca)2(en)]n的合成，结构和磁性(英)

A new nickel(Ⅱ)-dicyanamide compound, [Ni(dca)₂(en)]_n (1) (dca=dicyanamide anion, [N(CN)₂]^-); en=ethylene diamine), has been synthesized and its structure has been determined by single crystal X-ray diffraction analysis. The crystal is monoclinic, space group P2₁/n with unit cell dimensions: a=0.694 3(1) nm, b=1.041 5(2) nm, c=1.4132(2) nm, and β=90.381°, Z=4, V=1.011 0(3) nm³. In this compound, the adjacent nickel atoms are connected by dca all in μ_1，5-bridging mode to form ladder-like units, which are linked with double dca bridges to generate a regular infinite stair-like structure. Temperature-dependent magnetic susceptibility was also characterized for this compound. CCDC: 208276.     

Synthesis and Crystal Structure of 3-Benzoyl-7,7-dimethyl-4-phenyl-2-phenylamino-4,6,7,8-tetrahydro-chromen-5-one

The title compound (C30H27NO3) was synthesized via a one-pot procedure starting from β-benzoylthioacetanilide, benzaldehyde and 5,5-dimethyl-1,3-cyclohexanedione, and its struc- ture was determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic system, space group P, with a = 6.325(2), b = 11.243(3), c = 17.553(4) , α = 87.306(4), β = 80.822(4), γ = 77.798(4)°, V = 1204.2(5) 3, Z = 2, Mr = 449.53, Dc = 1.240 g/cm3, μ = 0.080 mm-1, F(000) = 476, the final R = 0.0459 and wR = 0.0970 for 2301 observed reflections with I > 2σ(I).