Über das Hexanitro‐äthan

Will, Wolfgang

doi:10.1002/cber.191404701154

Cited by 13 publications

(6 citation statements)

References 2 publications

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“…Early studies of α‐halogen derivatives of trinitromethane have demonstrated the pseudohalogenic nature of the trinitromethyl moiety 1. Further experimental evidence supporting this behavior as a pseudohalogen are the discoveries of the corresponding strong acid HC(NO 2 ) 3 ,2 various metal salts like K[C(NO 2 ) 3 ] and Ag[C(NO 2 ) 3 ],2b pseudointerhalogen compounds such as NCC(NO 2 ) 3 3 and N 3 C(NO 2 ) 3 ,4 as well as its dimer hexanitroethane 5. Furthermore, the existence of the halogenotrinitromethanes HalC(NO 2 ) 3 (Hal=F, Cl, Br, I) confirm this assumption.…”

Section: Introductionmentioning

confidence: 89%

Halogenotrinitromethanes: A Combined Study in the Crystalline and Gaseous Phase and Using Quantum Chemical Methods

Klapötke

Krumm

Moll

et al. 2014

Chemistry A European J

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The halogenotrinitromethanes FC(NO2 )3 (1), BrC(NO2 )3 (2), and IC(NO2)3 (3) were synthesized and fully characterized. The molecular structures of 1-3 were determined in the crystalline state by X-ray diffraction, and gas-phase structures of 1 and 2 were determined by electron diffraction. The Hal-C bond lengths in F-, Cl-, and Br-C(NO2 )3 in the crystalline state are similar to those in the gas phase. The obtained experimental data are interpreted in terms of Natural Bond Orbitals (NBO), Atoms in Molecules (AIM), and Interacting Quantum Atoms (IQA) theories. All halogenotrinitromethanes show various intra- and intermolecular non-bonded interactions. Intramolecular N⋅⋅⋅O and Hal⋅⋅⋅O (Hal=F (1), Br (2), I (3)) interactions, both competitors in terms of the orientation of the nitro groups by rotation about the C-N bonds, lead to a propeller-type twisting of these groups favoring the mentioned interactions. The origin of the unusually short Hal-C bonds is discussed in detail. The results of this study are compared to the molecular structure of ClC(NO2 )3 and the respective interactions therein.

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Section: Introductionmentioning

confidence: 89%

Halogenotrinitromethanes: A Combined Study in the Crystalline and Gaseous Phase and Using Quantum Chemical Methods

Klapötke

Krumm

Moll

et al. 2014

Chemistry A European J

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“…Halogenated trinitromethane compounds (HTC) which are known as explosives and propellants are also of interest from the fundamental viewpoint. [1][2][3] Indeed, the specific structural organization of these compounds with an electronegative halogen and three nitro groups linked by a common carbon atom [4][5][6] leads to non-trivial mutual atomic influence. Unfortunately, the current interpretation of non-covalent intramolecular interactions in these systems may not seem satisfactory now.…”

Section: Introductionmentioning

confidence: 99%

An anatomy of intramolecular atomic interactions in halogen-substituted trinitromethanes

Барташевич

Pendás

Tsirelson

2014

Phys. Chem. Chem. Phys.

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The intramolecular interactions in substituted trinitromethanes, XC(NO2)3 (X = F, Cl, I, H) are studied and clarified by using a combination of the Quantum Theory of Atoms in Molecules (QTAIM), the non-covalent interaction analysis and the Interacting Quantum Atoms (IQA) methods. The stretching vibration modes are formed by the concerted displacements of atoms involved in the covalent bonds showing the significant multiatomic influence in substituted trinitromethanes. In agreement with that, the arrangement of the local reduced density gradient minima indicates that the electron density favors the non-covalent intramolecular interactions X···O and N···O. However, the corresponding QTAIM bond paths are not formed; instead, contacts, which we call uncompleted links in this context, are accompanied by "quasi-bonding channels" corresponding to the λ2() ≤ 0 regions on the sign[λ2(r)]ρ(r) contour maps. The intramolecular IQA energy contributions signal the appreciable electron exchange between the pairs of atoms associated with potential atomic interactions or the bond-path-free non-covalent links. The IQA analysis shows that the electrostatic term destabilizes FC(NO2)3 and distinctly stabilizes IC(NO2)3, whereas it is close to neutral in ClC(NO2)3. The exchange energy between the X atom and the NO2 groups, in contrast, stabilizes all the molecules.

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“…Understanding the mutual interactions between atoms and functional groups is crucial for the control of chemical reactions and structural properties.T he study of simple yet extreme examples is therefore af undamental challenge,i n particular if the behavior of such systems deviates from the expected one.T etranitromethane (C(NO 2 ) 4 ,T NM) constitutes such an example.I ti so ne of only six experimentally established pernitro carbon compounds,t he derivatives of methane [C(NO 2 ) 4 ], ethane [C 2 (NO 2 ) 6 ], [1] ethene [C 2 -(NO 2 ) 4 ], [2] benzene [C 6 (NO 2 ) 6 ], biphenyl [C 12 (NO 2 ) 10 ], [3] and cubane [C 8 (NO 2 ) 8 ]. [4] TNM is well-known (m.p.1 3 8 8C, b.p.…”

mentioning

confidence: 99%

Tetranitromethane: A Nightmare of Molecular Flexibility in the Gaseous and Solid States

et al. 2017

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After numerous attempts over the last seven decades to obtain a structure for the simple, highly symmetric molecule tetranitromethane (C(NO ) , TNM) that is consistent with results from diffraction experiments and spectroscopic analysis, the structure has now been determined in the gas phase and the solid state. For the gas phase, a new approach based on a four-dimensional dynamic model for describing the correlated torsional dynamics of the four C-NO units was necessary to describe the experimental gas-phase electron diffraction intensities. A model describing a highly disordered high-temperature crystalline phase was also established, and the structure of an ordered low-temperature phase was determined by X-ray diffraction. TNM is a prime example of molecular flexibility, bringing structural methods to the limits of their applicability.

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Über das Hexanitro‐äthan

Cited by 13 publications

References 2 publications

Halogenotrinitromethanes: A Combined Study in the Crystalline and Gaseous Phase and Using Quantum Chemical Methods

Halogenotrinitromethanes: A Combined Study in the Crystalline and Gaseous Phase and Using Quantum Chemical Methods

An anatomy of intramolecular atomic interactions in halogen-substituted trinitromethanes

Tetranitromethane: A Nightmare of Molecular Flexibility in the Gaseous and Solid States

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