The dimerization of radical anions of aromatic carboxylic acids competing with the self-protonation reaction

Quantum-chemical calculations (CNDO/2) of the theoretical relationship between the rate constants for the dimerization and self-protonation of radical anions show that dimer formation in the one-electron electroreduction of aromatic carboxylic acids (benzoic (1), 1-naphthoic (2), and 9-anthroic (3) is most probable for1. It is established that during the constant potential electrolysis (CPE) of1 a mixture of “head-to-tail” dimers is formed in the presence of 0.1M Bu₄NClO₄ (DMF). Their ratio depends on the amount of electricity passed through the solution. The CPE of 2 in the presence of 20 % H₂O affords 1,4-dihydro-1-naphthoic acid in up to 70 % yield. The high yield (∼70 %) of 9,10-dihydro-9-anthroic acid during the CPE of 3 can be accounted for by the decomposition of the dimeric product followed by protonation of the anionic species. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1735–1738, October, 1993.     

1H NMR isotope shifts arising from the substitution of 12C by 13C: application to polycyclic aromatic hydrocarbon anions

Isotope shifts are a well-established tool for structural analysis by NMR. The substitution of a protium with a deuterium is the most widely studied of these effects. However, such studies call for specific deuteration that requires complex synthetic techniques owing to the low natural abundance of deuterium. ¹³C occurs at a higher natural abundance and couples strongly with its attached proton. We have developed and refined a method to reliably observe these much smaller shifts without needing to resort to chemical synthesis. We show that carbon induced isotope shifts reflect structural features. Copyright © 2001 John Wiley & Sons, Ltd.     

Aromaticity of giant polycyclic aromatic hydrocarbons with hollow sites: super ring currents in super-rings

We present a systematic theoretical study based on semi-empirical, Hartree-Fock (HF), and density functional theory (DFT) models of a series of polycyclic aromatic hydrocarbons (PAHs) that exhibit hollow sites. In this study we focus particularly on the magnetic criteria of aromaticity, namely (1)H NMR and nucleus-independent chemical shifts (NICS), and on their relationships with other electronic properties. The computed shifts and NICS indices indicate that an external magnetic field induces exceptionally strong ring currents in even-layered PAH doughnuts, in particular in the layer directly adjacent to the central hole of double-layered compounds. These exceptionally strong ring currents also correlate with particularly small HOMO-LUMO gaps and electronic excitation energies and to abnormally high polarizabilities, indicating in turn that these compounds have a more pronounced metallic character. Comparison is made with further depictions of aromaticity in these systems and in [18]-[66]annulene rings by employing topological, structural, and energetic criteria.     

An insight into the local aromaticities of polycyclic aromatic hydrocarbons and fullerenes

In this work we quantify the local aromaticity of six-membered rings in a series of planar and bowl-shaped polycyclic aromatic hydrocarbons (PAHs) and fullerenes. The evaluation of local aromaticity has been carried out through the use of structurally (HOMA) and magnetically (NICS) based measures, as well as by the use of a new electronically based indicator of aromaticity, the para delocalization index (PDI), which is defined as the average of all the Bader delocalization indices between para-related carbon atoms in six-membered rings. The series of PAHs selected includes C(10)H(8), C(12)H(8), C(14)H(8), C(20)H(10), C(26)H(12), and C(30)H(12), with benzene and C(60) taken as references. The change in the local aromaticity of the six-membered rings on going from benzene to C(60) is analyzed. Finally, we also compare the aromaticity of C(60) with that of C(70), open [5,6]- and closed [6,6]-C(60)NH systems, and C(60)F(18).     

Oxidative dimerization of aromatic amines using tBuOI: entry to unsymmetric aromatic azo compounds

It's all the hype: An oxidative dimerization reaction of aromatic amines utilizing tert-butyl hypoiodite (tBuOI) under mild reaction conditions leads to aromatic azo compounds. The method allows access to unsymmetric aromatic azo compounds, which are difficult to prepare by conventional synthetic methods, in a selective manner.     

Reductive activation of arenes

Stable cyanomethylcyclohexadienyl anions generated in two-electron reduction of isomeric tolunitriles by potassium in liquid ammonia were detected by NMR spectroscopy. The chemical shifts in these anions were obtained from density functional (PBE/3z) quantum chemical calculations and the electron density distributions for the anions were calculated in the framework of the NBO approach at the HF/6-31+G* level of theory. The experimental and calculated δ_C values are in good agreement. Changes in the δ_C values on going from the starting nitriles to the corresponding anions are linearly related to the calculated π-electron densities on the pentadienyl ring carbon atoms. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 940–944, June, 2006.     

多环芳烃水中溶解度的理论计算

建立了计算多环芳烃水中溶解度的数学表达式，用量子化学方法计算了7个多环芳烃的水中溶解度，计算结果与实验测定结果相符合．多环芳烃处于水体内体系状态能量愈高，其溶解度愈小，多环芳烃中的碳氢基团越多，溶解度越小．此时体系中的溶质呈单分子态，而不是聚集态．     

C2 isomers of C84F40 and C84F44 are cuboid and contain benzenoid and naphthalenoid aromatic patches

A 1:1 mixture of C84F40 and C84F44, both derived from the D2(IV) isomer, has been isolated from the fluorination of [84]fullerene with either MnF3 or CoF3 at 500 degrees C. The 1D and 2D COSY 19F NMR spectra showed that each derivative is cuboid, having benzenoid rings at four of the six octahedral sites; the two remaining sites have naphthalenoid rings for C84F40, and two slightly offset benzenoid rings for C84F44. The benzenoid rings each have six adjacent sp3-hybridised carbon atoms whilst the naphthalenoid moieties have eight, thus facilitating full delocalisation. In terms of the number and size of aromatic patches, C84F44 is the most aromatic fullerene derivative yet isolated.     

Samarium-induced convenient reductive dimerization of aromatic ketones in aqueous methanol: a mechanistic approach

Samarium metal has been used for the reductive dimerization of aromatic ketones in the presence of additives; the most probable mechanism has been advanced to explain the diastereoselectivity of this dimerization reaction.     

Reductive dimerization of dithianylium salts and fluorodesulfuration: a new synthetic approach to tetrafluoroethylene substructures

The reductive dimerization of dithianylium ions, followed by oxidative fluorodesulfuration, opens a convenient access to a variety of 1,2-disubstituted tetrafluoroethylene derivatives. A similar method leads to hexafluorodiacetyl, a potential building block for fluorinated heterocycles.     

The delocalization index as an electronic aromaticity criterion: application to a series of planar polycyclic aromatic hydrocarbons

This work introduces a new local aromaticity measure, defined as the mean of Bader's electron delocalization index (DI) of para-related carbon atoms in six-membered rings. This new electronic criterion of aromaticity is based on the fact that aromaticity is related to the cyclic delocalized distribution of pi-electrons. We have found that this DI and the harmonic oscillator model of aromaticity (HOMA) index are strongly correlated for a series of six-membered rings in eleven planar polycyclic aromatic hydrocarbons. The correlation between the DI and the nucleus-independent chemical shift (NICS) values is less remarkable, although in general six-membered rings with larger DI values also have more negative NICS indices. We have shown that this index can also be applied, with some modifications, to study of the aromaticity in five-membered rings.     

1,x-elimination reactions: extending the limits of a classical organic reaction

Alpha,omega-dibromo derivatives in which the two terminal carbon atom are separated by an unsaturated spacer unit ("pi spacer") undergo 1,x-elimination reactions (with x=6, 8, 10, and 14), using Mori's reagent (nBu3SnSiMe3/CsF). The resulting cumulenic intermediates cyclodimerize in a subsequent step yielding novel macrocyclic acetylenic and bridged aromatic compounds (cyclophanes). Thus 1,6-eliminations were carried out with dibromide 17 to yield 1,3,7,9-cyclododecatetrayne (20) and with benzylbromide 24 to provide cyclophanes 26 and 27. By 1,8-eliminations the 16-membered macrocycle 33 could be prepared from enediyne 31, the benzannelated 1,5-cyclooctadiyne 41 from dibromide 38, and a mixture of cyclophanes 45 and 46 from the precursor 43. 1,10-Eliminations were carried out successfully with dibromides 47, 50, and 53 yielding the corresponding unsaturated cyclophanes ("cyclophynes") 49, 52, and 55. The influence of the solvent on the cyclodimerization 47-->49 was investigated, with acetonitrile providing the highest yields. The heterophanes 59 a and b were obtained by 1,10-elimination of the precursor dibromides 57 a and b, and in an elimination experiment involving a 1:1 mixture of the dibromides 50 and 57 b the "mixed dimer" 60 was isolated, besides the homodimers 52 and 59 b. The method reached its limits with the 1,14-elimination of 68, 70, and 74 providing the cyclophanes 69, 71, and 75 in varying amounts. Two final debrominations with 76 and 77, which in principle could undergo 1,16- and 1,20-eliminations reactions, respectively, failed. The structures of the new cyclophanes 49, 50, 59 a, and 59 b were established by X-ray structural analysis; all other structure assignments rest on the usual spectroscopic and analytical data.     

Adsorption of polycyclic aromatic hydrocarbons onto graphyne: Comparisons with graphene

Density functional theory calculations were implemented to expand the knowledge about graphyne and its interaction with polycyclic aromatic hydrocarbons (PAHs). Due to the porous character of graphyne, the adsorption strength of PAHs onto graphyne surfaces is expected to be lower with respect to graphene (a perfect π‐extended system). However, there are not quantitative evidences for this assumption. This work shows that the adsorption strength of adsorbed PAHs onto γ‐graphyne nanosheets (GY) is weakened in 12 ? 23% with respect to the adsorption onto graphene, with a decrease of 10 ? 20% in the dispersive interactions. The adsorption energies (in eV) of the GY–PAH systems can be straightforward obtained as E _ads/eV≈0.033N _H + 0.031N _C, where N _H and N _C is the number of H and C atoms in the aromatic molecule, respectively. This equation predicts the binding energy of graphene–graphyne bilayers with a value of ～31 meV/atom. Analysis of the electronic properties shows that PAHs behaves as n‐dopants for GY, introducing electrons in GY and also reducing its bandgap in up to ～0.5 eV. Strong acceptor or donor substituted PAHs decrease the bandgap of γ‐graphyne in up to ～0.8 eV, with changes in its valence or conduction band, depending on the chemical nature of the adsorbate. Finally, these data will serve for future studies related to the bandgap engineering of graphyne surfaces by nonaggressive molecular doping, and for the development of graphyne‐based materials with potential applications in the removal of persistent aromatic pollutants.     

Synthesis of [3]Rotaxanes that Utilize the Catalytic Activity of a Macrocyclic Phenanthroline–Cu Complex: Remarkable Effect of the Length of the Axle Precursor

[3]Rotaxanes, which consist of one macrocyclic phenanthroline compound and two axle components, were prepared by the oxidative dimerization of an alkyne compound with bulky tris[4′‐cyclohexyl‐(1,1′‐biphenyl)‐4‐yl]methyl blocking group. The catalytic activity of a macrocyclic phenanthroline–Cu complex was utilized to thread the two axle components inside the ring. The alkyne compound with chain of 15 or 20 methylene groups gave [3]rotaxanes in high yields, whereas the axle with a chain of six methylene groups afforded a [3]rotaxane in very poor yield. We also examined the effect of the ring size on the synthesis of [3]rotaxanes. [3]Rotaxanes were not isolated when a macrocyclic phenanthroline compound with a smaller ring size was used.