Aromatic C-nitroso Compounds

Vančik, Hrvoj

doi:10.1007/978-94-007-6337-1

Cited by 55 publications

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“…[1][2][3] They exist in two different forms, as nitroso compounds (monomers), and E-or Zazodioxy compounds (dimers or polymers). [4,5] In the solid state, most aromatic C-nitroso compounds appear in the azodioxy form, but can be converted to stable or metastable monomeric forms by dissolution in organic solvents, heating, or by UV irradiation at cryogenic temperatures. [5] An important feature of the nitroso/azodioxy system is that the two forms can be easily distinguished by spectroscopic methods (UV / Vis, NMR, IR, etc.…”

Section: Introductionmentioning

confidence: 99%

“…), which facilitates kinetic measurements. [4] 1,4-Dinitrosobenzene has been investigated because it is, next to 1,3-dinitrosobenzene, the simplest aromatic Cdinitroso compound capable of polymerization. It has been found that by deposition of 1,4-dinitrosobenzene vapor onto the surface cooled to 12 K produces a solid layer consisting only of the nitroso monomer.…”

Section: Introductionmentioning

confidence: 99%

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Polymerization of 1,4-dinitrosobenzene: Kinetics and Submicrocrystal Structure

et al. 2017

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In this study, the structure of the polycrystalline poly(l,4-phenyleneazine N,N-dioxide) was investigated by Scanning Electron Microscopy and related with the previously calculated molecular structure. Kinetics of polymerization of 1,4-dinitrosobenzene, prepared by both cryogenic UV photolysis and in vacuo deposition were measured by time-resolved FT-IR spectroscopy. Acquired data was analyzed by curve fitting with the standard Avrami-Erofeev and two-step consecutive reactions models. Activation parameters were calculated from Arrhenius and Eyring-Polanyi equations, for both models. The results obtained by using the two models, along with the goodness-of-fit parameters, were compared. It was shown that both bulk-based and reaction-based models can be used to adequately describe solid-state chemical reaction kinetics. Furthermore, a two-step consecutive reactions model is a suitable alternative to the most commonly used AvramiErofeev model.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polymerization of 1,4-dinitrosobenzene: Kinetics and Submicrocrystal Structure

et al. 2017

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“…The model, which we have developed is based on the reactions of the nitrosobenzene derivatives in the crystal phase [13,[25][26][27][28][29][30][31]. Such a system is simple because it includes the formation and/or breaking of only one chemical bond between two nitrogen atoms during the dimerization of C-nitroso compounds to the Z-or E-azodioxy dimers, or their subsequent dissociation to the starting monomers (Scheme 1) [32][33][34][35][36][37][38][39].…”

Section: Experimental and Conceptual Modelmentioning

confidence: 99%

Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

Biljan

Vančik

2017

Crystals

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This review is focused on the dimerization and dissociation of aromatic C-nitroso compounds and their dimers, the reactions that could be used as a convenient model for studying the thermal organic solid-state reaction mechanisms. This molecular model is simple because it includes formation or breaking of only one covalent bond between two nitrogen atoms. The crystalline molecular solids of nitroso dimers (azodioxides) dissociate by photolysis under the cryogenic conditions, and re-dimerize by slow warming. The thermal re-dimerization reaction is examined under the different topotactic conditions in crystals: disordering, surface defects, and phase transformations. Depending on the conditions, and on the molecular structure, aromatic C-nitroso compounds can associate to form one-dimensional polymeric structures and are able to self-assemble on gold surfaces.

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“…The reaction is often accompanied by formation of dimerization products, which has been the focus of many recent studies. [4][5][6][7] The reduction of aromatic nitro compounds has been extensively studied using spectroscopic, electrochemical and, in recent years, computational approaches. [8][9][10][11][12][13][14] Although the available data strongly suggests that the reduction mechanism includes free radicals, its detailes, with identification and characterization of all involved species, have not unequivocally been established.…”

Section: Introductionmentioning

confidence: 99%

Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds

Tomin¹,

Rončević²,

Mihalić³

2016

Croat. Chem. Acta

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Abstract:The main goal of this paper is to find an adequate level of theory for the computational investigation of the reduction mechanisms of aromatic nitro-and nitroso compounds. To this end, five standard reduction potentials of nitro-and nitrosobenzene in three different solvents and four pKa values of species involved in the mechanism were compared with the values calculated at different DFT and CBS-X levels of theory. Out of fourteen tested functionals, five showed good linear correlation between calculated and experimental ΔrG° values. However, at all explored levels of theory, the calculated ΔrG° values systematically deviate from the experimental ones, indicating the necessity of better description of solvation effects for charged species, possibly via a cluster-continuum approach.

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Aromatic C-nitroso Compounds

Cited by 55 publications

References 0 publications

Polymerization of 1,4-dinitrosobenzene: Kinetics and Submicrocrystal Structure

Polymerization of 1,4-dinitrosobenzene: Kinetics and Submicrocrystal Structure

Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds

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