Ferrocenyl Ionic Compounds Based on 5‐Ferrocenyl‐1<i>H</i>‐tetrazole. Synthesis, Characterization, Migration, and Catalytic Effects During Combustion

Gao, Xiaoni; An, Ting; Li, Jizhen; Zhao, Fengqi; Fan, Xuezhong; Li, Xinyan; Zhang, Guofang; Gao, Ziwei

doi:10.1002/zaac.201500690

Cited by 16 publications

(2 citation statements)

References 26 publications

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“…This means that the corresponding structures could not be optimized because undesirable dihedral angle changes occur for the other ϕ. Despite the presence of a shallow basin in the PES, the planar conformers should not be neglected because they are indeed observed in the crystalline phases, − albeit at a low population.…”

Section: Resultsmentioning

confidence: 99%

Comprehensive Conformational and Rotational Analyses of the Butyl Group in Cyclic Cations: DFT Calculations for Imidazolium, Pyridinium, Pyrrolidinium, and Piperidinium

et al. 2016

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The flexibility and conformational variety of the butyl group in cations of ionic liquids (ILs) play an important role in dictating the macroscopic and microscopic properties of ILs. Here we calculate potential energy surfaces for the dihedral angles of the butyl group in four different types of cyclic cations, imidazolium, pyridinium, pyrrolidinium, and piperidinium, using the density functional theory method. The calculation results highlight the role of the butyl group in these cations by comparison of five-membered and six-membered rings, and of aromatic and alicyclic rings, in terms of stable conformations and rotational barriers. A striking result is that the butyl group rotation in pyrrolidinium induces pseudorotation of the ring whereas such a phenomenon does not occur in piperidinium. This difference is thought to be because of the relationship in rotational activation energy between the butyl group (10-40 kJ mol) and the ring (<6 kJ mol for pyrrolidinium and 40-50 kJ mol for piperidinium). The calculated stable conformers are compared with the ones observed in crystals recorded in the Cambridge Structural Database. Although conformers with lower calculated energy generally have higher chances to be experimentally observed, roughly independent of the cation structure, some calculated conformers deviate from this trend and show very low population. It is found that not only low energy but also high rotational activation energy (i.e., long lifetime) is required to observe conformers in crystalline states. In the last part of this article, to identify conformers in real systems, the applicability of the calculated Raman bands of cations with different butyl group conformations is discussed.

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Section: Resultsmentioning

confidence: 99%

Comprehensive Conformational and Rotational Analyses of the Butyl Group in Cyclic Cations: DFT Calculations for Imidazolium, Pyridinium, Pyrrolidinium, and Piperidinium

et al. 2016

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“…The twisted conformation of the cation of (II) and the charge delocalization in its CN 3 planes appear to result from the double protonation. Indeed, the two guanidine groups in monoprotonated KABLEH are almost coplanar (the angle between the normals to the two planes is about 9.83 ) (Gao et al, 2016). The N-C13-N angles of KABLEH are in the range 117.0 (7)-127.2 (7) and show a deviation of this CN 3 plane from ideal trigonal planarity.…”

Section: Figurementioning

confidence: 97%

Formaldehyde–aminoguanidine condensation and aminoguanidine self-condensation products: syntheses, crystal structures and characterization

et al. 2018

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Guanidine is the functional group on the side chain of arginine, one of the fundamental building blocks of life. In recent years, a number of compounds based on the aminoguanidine (AG) moiety have been described as presenting high anticancer activities. The product of condensation between two molecules of AG and one molecule of formaldehyde was isolated in the protonated form as the dinitrate salt (systematic name: 2,8-diamino-1,3,4,6,7,9-hexaazanona-1,8-diene-1,9-diium dinitrate), CHN·2NO, (I). The cation lacks crystallographically imposed symmetry and comprises two terminal planar guanidinium groups, which share an N-C-N unit. Each cation in (I) builds 14 N-H...O hydrogen bonds and is separated from adjacent cations by seven nitrate anions. The AG self-condensation reaction in the presence of copper(II) chloride and chloride anions led to the formation of the organic-inorganic hybrid 1,2-bis(diaminomethylidene)hydrazine-1,2-diium tetrachloridocuprate(II), (CHN)[CuCl], (II). Its asymmetric unit is composed of half a diprotonated 1,2-bis(diaminomethylidene)hydrazine-1,2-diium dication and half a tetrachloridocuprate(II) dianion, with the Cu atom situated on a twofold rotation axis. The planar guanidinium fragments in (II) have their planes twisted by approximately 77.64 (5)° with respect to each other. The tetrahedral [CuCl] anion is severely distorted and its pronounced `planarity' must originate from its involvement in multiple N-H...Cl hydrogen bonds. It was reported that [CuCl] anions, with a trans-Cl-Cu-Cl angle (Θ) of ∼140°, are yellow-green at room temperature, with the colour shifting to a deeper green as Θ increases and toward orange as Θ decreases. Brown salt (II), with a Θ value of 142.059 (8)°, does not fit the trend, which emphasizes the need to take other structural factors into consideration. In the crystal of salt (II), layers of cations and anions alternate along the b axis, with the minimum Cu...Cu distance being 7.5408 (3) Å inside a layer. The structures of salts (I) and (II) were substantiated via spectroscopic data. The endothermic reaction involved in the thermal decomposition of (I) requires additional oxygen. The title salts may be useful for the screening of new substances with biological activity.

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Mono‐ and Dinuclear Ferrocenyl Ionic Compounds with Polycyano Anions. Characterization, Migration, and Catalytic Effects on Thermal Decomposition of Energetic Compounds

Shao

et al. 2016

Zeitschrift anorg allge chemie

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Neutral ferrocene‐based burning rate (BR) catalysts show strong migration trends and volatility during long‐time storage and curing of the composite solid propellants. To reduce these disadvantages thirty‐two ferrocenyl quaternary ammonium compounds, paired with polycyano anions, were synthesized and characterized by 1H NMR, 13C NMR, and UV/Vis spectroscopy, as well as elemental analysis. Additionally, crystal structures of eight compounds were confirmed by single‐crystal X‐ray diffraction. TG and DSC analyses indicated that the compounds containing 1,1,2,3,3‐pentacyanopropenide anions show high thermal stability. Cyclic voltammetry studies suggested that they are quasi‐reversible or irreversible redox systems. Anti‐migration tests verified that the tested compounds show very low migration tendency and some of them exhibit no migration after 30 days aging at 70 °C. Their catalytic efficiency in the thermal decomposition of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,2,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) were examined by DSC analyses. The results revealed that most of the compounds exhibit distinct effects on the thermal degradation of AP and RDX. Two compounds have good catalytic ability in the thermal decomposition of HMX, representing rare examples of the reported ferrocenyl ionic compounds, which display catalytic property during combustion of HMX.

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Ferrocenyl Ionic Compounds Based on 5‐Ferrocenyl‐1H‐tetrazole. Synthesis, Characterization, Migration, and Catalytic Effects During Combustion

Cited by 16 publications

References 26 publications

Comprehensive Conformational and Rotational Analyses of the Butyl Group in Cyclic Cations: DFT Calculations for Imidazolium, Pyridinium, Pyrrolidinium, and Piperidinium

Comprehensive Conformational and Rotational Analyses of the Butyl Group in Cyclic Cations: DFT Calculations for Imidazolium, Pyridinium, Pyrrolidinium, and Piperidinium

Formaldehyde–aminoguanidine condensation and aminoguanidine self-condensation products: syntheses, crystal structures and characterization

Mono‐ and Dinuclear Ferrocenyl Ionic Compounds with Polycyano Anions. Characterization, Migration, and Catalytic Effects on Thermal Decomposition of Energetic Compounds

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