C‐nitroso compounds. Part XXIII: Cis/trans‐isomerisation of aliphatic azodioxy compounds (dimeric nitrosoalkanes)

Wajer, Th. A. J. W.; Boer, Th. J. de

doi:10.1002/recl.19720910508

Cited by 19 publications

(8 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The first kinetic study of the isomerization of dimers of nitrosoalkanes was published by Chaudhry and Gowenlock in 1968, but interpretation of their results was complicated by the competing formation of oximes by tautomerism . In 1972, Wajer and de Boer reported that the formation of oximes could be suppressed in acetonitrile, allowing them to study the cis–trans isomerization of the dimers of nitrosomethane and nitrosocyclohexane . Their kinetic data proved to be consistent with the mechanism of dissociation–association.…”

Section: Mechanism Of Dimerizationmentioning

confidence: 79%

“…128 In 1972, Wajer and de Boer reported that the formation of oximes could be suppressed in acetonitrile, allowing them to study the cis− trans isomerization of the dimers of nitrosomethane and nitrosocyclohexane. 129 Their kinetic data proved to be consistent with the mechanism of dissociation−association. Although this study demonstrated that the isomerization of azodioxides occurs preferentially by dissociation into nitroso monomers, the basis for this preference remained unclear.…”

Section: Cis−trans Isomerization Of Azodioxidesmentioning

confidence: 99%

See 1 more Smart Citation

Dimerization of Aromatic C-Nitroso Compounds

2016

View full text Add to dashboard Cite

Aromatic C-nitroso compounds (Ar-N═O) and related species have a rich chemical history, and they continue to interest researchers in many fields. Among the most distinctive and puzzling properties of these compounds is their ability to dimerize reversibly to form azodioxy compounds. The present review subjects this intriguing phenomenon to comprehensive analysis. All aspects of the subject are examined in detail, including the structures of monomeric and dimeric forms, the mechanism of dimerization, features that favor or disfavor dimerization, thermodynamic and kinetic factors, dimerization under specific conditions (including in solution, in the solid state, and on surfaces), and the special associative behavior of dinitroso and polynitroso compounds. By summarizing the current state of knowledge, the review promises to spur further advances in the evergreen field of C-nitroso chemistry, including the discovery of new ways to exploit the reversible dimerization of nitrosoarenes.

show abstract

Section: Mechanism Of Dimerizationmentioning

confidence: 79%

Section: Cis−trans Isomerization Of Azodioxidesmentioning

confidence: 99%

Dimerization of Aromatic C-Nitroso Compounds

2016

View full text Add to dashboard Cite

show abstract

“…C-nitrosobenzenes can exist in two different forms, as monomers or dimers (azodioxides). Broad literature is available on dimerization of nitrosobenzenes. − Because the energy of an azodioxide (O)NN(O) bond is of the same order of magnitude as a hydrogen bond, its formation strongly depends on the conditions of the environment. In principle, dimers can be formed either in the crystal form or in solution by lowering temperature. , Previous studies revealed that if the molecules are favorably oriented in the crystal lattice with their nitroso groups properly oriented in the vicinity then they would readily form azodioxides in crystals. , Such dimers can undergo photodissociation to monomers in crystals only at low temperatures .…”

Section: Introductionmentioning

confidence: 99%

Dimerization of Nitrosobenzene Derivatives on an Au(111) Surface

et al. 2011

View full text Add to dashboard Cite

In this study, we have investigated the ability of C-nitrosobenzenes to dimerize on an Au(111) surface and form ordered self-assembled bilayers (SABs). Use of scanning tunneling microscopy (STM) revealed that nitrosobenzene derivatives are able to form both well-ordered monolayers (SAMs) and bilayers (SABs). High-resolution STM images showed that within SAM regions molecules are arranged into hexagonal structures. Moir e-type superstructure with a periodicity of 1.5 nm was observed, indicating a 3 √ 3 Â 3 √ 3 molecular arrangement. Molecularly resolved STM images showed that within bilayers molecules are also arranged into hexagonally ordered structures at intermolecular spacing of ∼0.4 nm. Furthermore, it was observed that the second layer is better ordered than the first one, probably because of the softer background. Use of atomic force microscopy (AFM), through measured height differences between monolayers and bilayers, further confirmed the formation of SABs. The results of the present study demonstrate that nitrosobenzenes represent convenient molecular models that can be used for systematic design and study of bilayers on metal surfaces. Besides the previously known properties of C-nitroso compounds to form dimers in crystals, here we have found a new situation under which these molecules dimerize, which is, in principle, a 2D crystallization.

show abstract

“…The liquid-state one-dimensional 1 H and 13 C NMR spectra (600.13 MHz for 1 H, 150.90 MHz for 13 C) were measured in CDCl 3 on a Bruker AV600 spectrometer at room temperature. Chemical shifts, in ppm, were referred to tetramethylsilane (TMS) as the internal standard.…”

Section: Nmr Spectroscopymentioning

confidence: 99%

“…In solid state, C -nitroso compounds are usually present as dimers, and in the solution there is an equilibrium between monomers and dimers. − In aromatic C -nitroso compounds at room temperature the equilibrium is usually shifted toward monomers, and Z - or E -dimers can be observed only at low temperatures. − Different behavior has been observed for 2-nitrosopyridines, where dimers can coexist with monomers even at room temperature.…”

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Calculations of Monomer–Dimer Equilibria of Aromatic C-Nitroso Compounds

et al. 2018

View full text Add to dashboard Cite

Monomer-dimer equilibria of nitrosobenzene and 2-nitrosopyridine in gas phase and solution were studied by range of quantum chemical methods in an attempt to find the level of theory suitable for modeling dimerization reactions of aromatic C-nitroso compounds in general. The best agreement with the experimental standard reaction Gibbs energies was obtained with a combination of double-hybrid density functionals B2PLYP-D3, PBE0DH, and DSD-PBEB86, and basis sets of triple-ζ quality. Of all other tested functionals, global hybrid PBE0 behaved equally well, and proved to be more than adequate for at least preliminary work. Other tested methods either produced inferior results (MP2, MP4(SDQ), CCSD, G4(MP2), CBS-QBS, CBS-APNO), or were too demanding for practical use (CCSD(T)). Analysis of computationally obtained thermodynamic data reveal intricate details of these reactions. Both E- and Z-dimers have several different conformers, which all have different solvation energies. While in the gas phase the nitrosobenzene E-dimer is more stable that its Z-form, in chloroform, the Z-form is more stable. Gas-phase dimerization entropies are large and negative, so these reactions are strongly temperature dependent. In some cases, like with 2-nitrosopyridines, entropy and enthalpy terms essentially cancel each other out, allowing structural and media effects to significantly influence dimerization equilibria.

show abstract

C‐nitroso compounds. Part XXIII: Cis/trans‐isomerisation of aliphatic azodioxy compounds (dimeric nitrosoalkanes)

Cited by 19 publications

References 36 publications

Dimerization of Aromatic C-Nitroso Compounds

Dimerization of Aromatic C-Nitroso Compounds

Dimerization of Nitrosobenzene Derivatives on an Au(111) Surface

Quantum Chemical Calculations of Monomer–Dimer Equilibria of Aromatic C-Nitroso Compounds

Contact Info

Product

Resources

About