Quantum chemical studies on the structures, properties and decomposition of the azido derivatives of trinitrobenzenes

The geometries,heats of formation and electronic structures of 15 azido-derivatives of 1,2,3-TNB (Ⅰ),1,2,4-TNB (Ⅱ) and 1,3,5-TNB (Ⅲ) have been studied using quantum chemical AMI method at HF level.The effect of azido substitution on the structures and properties of TNBs has been discussed and the relative stability of the title compounds has been established.The processes of the decomposition of the title compounds by breaking C-NO2,C-N3 and CN-N2 bonds are investigated at UHF-AM1 level.It is shown that the decomposition of the title compounds may be initiated by the cleavage of both C-NO2 and N-N2 bonds.     

Crystal structure and spectroscopic study of di-μ(1,1)-azido-di-μ(0,0-nitrato)tetrakis(3,5-lutidine)dicopper(II), [Cu(N3) (NO3) (3,5-lutidine)2]2

A mixed ligand 12 complex of copper(II) azide with 3,5-lutidine, namely di-(1,1)-azido-di(0,0)-nitrato)tetrakis(3,5-lutidine)dicopper(II) has been prepared and characterized by X-ray crystallographic and spectroscopic methods. The dimeric molecule, which possesses a crystallographic inversion center, contains two(1,1) bridging azido ligands. Each copper(II) atom in the cyclic Cu₂N₂ unit is further coordinated by two oxygen atoms from two(0,0-nitrato) bridges at Cu-O distances of 2.465(3) and 2.568(3) Å and two nitrogen atoms from the lutidine molecules [Cu-N=2.003(3) and 2.012(3) Å] to give a distorted tetragonal bipyramid. Both azido ligands are linear [N-N-N angle=179.0(4) and asymmetric N-N=1.207(4) and N-N=1.135(5) Å]. The azido bridges produce a rather short Cu Cu distance of 3.013(2) Å. Infrared and electronic data are presented and discussed.     

Supramolecular lead(II) azide complex of 2,6-diacetylpyridine dihydrazone: synthesis,molecular structure,and biological activity

The complex of 2,6-diacetylpyridinedihydrazone (L) with lead(II) and azide has been characterized by elemental analyses, FTIR, and single-crystal X-ray analysis. The Pb(C₉H₁₃N₁₁) (1) crystallized in the monoclinic space group C2/c. The coordination of 1 exhibits a gap around the lead(II), possibly occupied by a stereochemically active electron lone pair on lead(II) resulting in a hemidirected complex. Antimicrobial activity of the complex is higher than the free ligand.     

One‐Pot and Convenient Conversion of 5‐Azidopyrazole‐4‐carboxaldehyde to Pyrazolo[3,4‐b]pyridines

A one‐pot and convenient synthesis of multisubstituted pyrazolo[3,4‐b]pyridines in moderate to high yields has been achieved by a two‐step reaction: diazo‐transfer of 5‐azido‐1‐phenylpyrazole‐4‐carboxaldehydes to ketones in ethanolic KOH to give 5‐amino‐1‐phenylpyrazole‐4‐carboxaldehyde and subsequent Friedlaender reaction of 5‐amino‐1‐phenylpyrazole‐4‐carboxaldehyde with ketones.     

The azido-tetrazole and diazo-1,2,3-triazole tautomerism in six-membered heteroaromatic rings and their relationships with aromaticity: Azines and perimidine

The properties of 28 molecules together with 12 transition states belonging to the series of azido-azines, tetrazolo-azines, diazo-azines, and 1,2,3-triazolo-azines have been studied at the B3LYP/6-31G(d), B3LYP/6-311++G(d,p) and, for 26 cases, at the G3B3 level. Energies, NICS and bond critical points were used to discuss the ring-chain tautomerism of these compounds in relation with the aromaticity of the azines (pyridine, pyrimidine, quinazoline, 1,3-diazapyrene, and perimidine) and the azoles (tetrazoles and 1,2,3-triazoles).     

3,5-Disubstituted 6H-pyrrolo[1,2-c][1,2,3]triazoles from Morita-Baylis-Hillman adducts of propargyl aldehydes

A simple method for synthesizing several 6H-pyrrolo[1,2-c][1,2,3]triazole derivatives having a methoxycarbonyl or an acetyl group at C-5 position and 7,8-dihydro-4H-[1,2,3]triazolo[1,5-a]indol-5(6H)-ones via an intramolecular 1,3-dipolar cycloaddition reaction of azido enynes, which were readily obtained from the Morita-Baylis-Hillman acetates of propargyl aldehydes with sodium azide, has been developed.     

An efficient peptide ligation using azido-protected peptides via the thioester method

Azido-protected Fmoc-Lys-OH (Fmoc-Lys(N₃)-OH) was synthesized from Fmoc-Lys-OH by the copper(II)-catalyzed diazo transfer method, and introduced to a peptide by the ordinary Fmoc-based solid-phase peptide synthesis. This azido peptide could be condensed with a peptide thioester by the Ag⁺-free thioester method without any significant side reactions. The azido group was easily reduced to an amino group by Zn powder after peptide condensation.     

X‐Ray Crystal Structures and Quantum Chemical Calculations of Tetraphenyl‐arsonium Tetraazidoaurate(III) and Azido(triphenylphosphine)Gold(I)

The single crystal X‐ray structure determinations are reported for [Ph₄As][Au(N₃)₄] ( 1 ) and Ph₃PAuN₃ ( 2 ). Compound 1 is an ionic species with a “windmill” shaped anion. It crystallizes in the monoclinic space group C2/c, a = 18.396(2), b = 6.2492(4), c = 23.555(2) Å; β = 107.98(1)°, Z = 4, R1_{(all data)} = 0.0227, wR2 = 0.0374. The lattice parameters of compound 2 , which crystallizes in the orthorhombic space group P2₁2₁2₁, are a = 10.9252(1), b = 11.5642(1), c = 13.0993(1) Å; Z = 4, R1_{(all data)} = 0.0176, wR = 0.0334. The experimentally obtained X‐ray data and vibrational frequencies of both compounds were compared with those calculated at B3LYP/LANL2DZ and B3LYP/SDD level of theory and for 1 also at the MP2/SDD level.     

叠氮桥对双核镍配合物磁性影响的密度泛函理论研究

结合对称性破损(BS)方法, 采用不同的密度泛函理论(DFT)对反铁磁性μ-1,3-N₃-Ni(II)叠氮配合物[LNi₂(N₃)](ClO₄)₂ (L=pyrazolate)的磁特性进行了研究. 结果显示, 杂化密度泛函理论(HDFT)的计算结果与实验数据非常吻合, 能够准确描述配合物的磁特性. 磁轨道研究结果表明, 配合物表现出较大的单占据轨道能量劈裂(0.93-0.99 eV), 显示配合物的单占据轨道去简并化程度较大, 且配合物中的2 个磁通道(叠氮基、配体pyrazolate)中都分别存在有氮原子之间的p轨道重叠, 这些都使得体系表现为反铁磁耦合作用. 另外, 配合物的磁性与叠氮桥和两金属离子间形成的二面角(τ, Ni-N-N-N-Ni)密切相关, τ从-55.38°逐渐变化到-1.5°的过程中, 其反铁磁性逐渐增强, 交换耦合常数(J_ab)的绝对值逐渐增大, 并在-11.95°处达到最大值(J_ab=-151.02 cm^-1).在此过程中, 配合物中叠氮桥及其所连接的2个Ni 离子与pyrazolate 基配体L^-中的2个桥原子N(4)、N(5)形成的七元环共平面性不断增强, 即共平面性会诱导增强体系的反铁磁相互作用.     

Syntheses,Structures and Characterization of Cobalt(II) and Cobalt(III) Complexes with N-Benzylated Polyamines and a Terminal Azido Ligand

Mononuclear cobalt(II) and cobalt(III) complexes, [Co(trenb)(N₃)]Cl (1) and [Co(dienb)(N₃)₂(OAc)] (2) (trenb = tris[2-(benzylamino)ethyl]amine, dienb = 1,9-diphenyl-2,5,8-triazanonane) were synthesized and characterized by elemental analyses, IR and electronic spectra. Their crystal structures were also determined by X-ray diffraction analyses. In Complex 1, cobalt(II) is five-coordinate trigonal bipyramidal with one azido nitrogen atom and four nitrogen donors of the tripodal ligand; the chloride interacts weakly with one of the secondary amino groups of trenb via a hydrogen bond. In Complex 2, cobalt(III) is in a distorted octahedral coordination environment, consisting of three nitrogen atoms of the amine ligand, two azide nitrogen atoms and an oxygen atom of the acetate ion; a six-membered ring involving the hydrogen bond may stabilize the complex, which maintains its solid geometry in DMF as indicated by the electronic spectrum.