Structure and Reactions of Aliphatic Bridged Bifunctional Radical Ions: Exploring Fine-Tuning in Radiation Chemistry

Bridged bifunctional molecules of general structure X (CH₂)_n Y are useful models for investigations into the effects of intra- and intermolecular interactions in primary radiation-induced processes, with a number of implications for radiation chemistry, radiobiology, and molecular electronics. This short Review presents an outline of recent studies on the structure and reactivity of aliphatic bifunctional radical ions in low-temperature matrices using EPR spectroscopy and quantum-chemical calculations. Both EPR data and DFT calculations for radical cations show that the delocalization of charge and spin density occurs if XY or X and Y have close electronic properties. If the difference in the ionization potentials between X and Y is large, localized radical cations are observed with ground-state properties close to those of the corresponding monofunctional species. Nevertheless, the remote second functional group may affect the photochemistry of such radical cations at a specific bridge length, probably due to intramolecular interactions in a certain conformation. The stabilization of bridged bifunctional radical anions containing two carbonyl groups was found to be very sensitive to the local environment, which may be described in terms of a microsolvation model at the MP2 level of theory. Two independent reactions pathways with excess electrons, yielding different types of localized radical anions, were demonstrated for asymmetrical bifunctional molecules. The obtained results and their implications are discussed in terms of fine-tuning effects in radiation-induced chemical processes in condensed phases.     

Electrooxidation of bromoalkanes on platinum in liquid hydrogen fluoride. Selective displacement of bromine by fluorine

Carbon—bromine bond cleavage was investigated in HF as a privileged route to the formation of electrophilic carbon ions and subsequent obtention of alkyl fluorides.Nucleophilic attack of fluoride ions on electrochemically generated radical cations, R—Br⁺, or carbenium ions, R⁺, proved selective and quantitative in the case of bromomethane, 1,2-dibromoethane, 1,2-dibromopropane, 1,3-dibromo propane and 1,2,3-tribromopropane.For bromoethane, 1-(or 2-)bromopropane, 1-(or 2-)bromobutane, 1-bromo-2-methyl propane and 1-bromo-3-methyl butane, the observed lack of halogenation selectivity is discussed in terms of radical side reactions.     

Electrochemical studies of selected regioregular oligooctylthiophenes in solution and in thin film solid state

Electrochemical studies of a series of regioregular 3-octylthiophene oligomers with 5-8 thiophene rings, chlorine end-capped at one α terminal position, have been conducted in solution and in thin film state. Results indicate gradual coalescing of the oxidation potentials of neutral and radical cation oligomer molecule, indicative of coming close to sufficient length of the molecule to allow for two separate radical cations to exist along its chain. With increasing number of thiophene rings in the molecule, further quasi-reversible oxidation reactions upon which trication and tetracation were formed have been observed at ever decreasing potentials. It was also observed that the oxidation of radical cations comes about more easily than that of electron-paired cations, the latter process being strongly dependent on the length of oligothiophene chain. Thin film electrochemistry revealed that the processes taking place during redox reactions differ from those in solution. Sharp oxidation peaks were observed which were attributed to conformational changes taking place in the oligomer molecules upon transition to the conductive form, alongside the film's oxidative doping process. To shed some light on the issue of charge carriers appearing in the film upon its oxidation, supplemental ESR spectroelectrochemical measurements were carried out and confirmed that, radical cations are generated in the film.     

Arene—onium cations—VI Electrode kinetics of the anodic formation of arene—sulphonium cations from bisarenesulphides

Electrode kinetic investigations (voltammetry at stationary electrodes, rotating ring—disc electrodes and rotating rod electrodes) of the anodic oxidation of bisanisole-, bismesitylene-, bisxylene-, bistoluene- and bisbenzenesulphide were performed in acetonitrile. Observed anodic half wave potentials increase in the given order. The S-radical cations of the bisarenesulphides form in a reversible one-electron oxidation step. The radical cations of bisanisole- and bismesitylenesulphide are unable to react, even with relatively strong bases like water, and they disproportionate to form the more reactive dications which react readily with different nucleophiles. The more reactive radical cations of bisxylene-, bistoluene- and bisbenzenesulphide react directly with nucleophiles, for instance with aromatic bases and with the more basic hydrocarbons (anisole, styrene). Participation of dications in their consecutive reactions cannot be detected. The anodic dimerization of these three bisarenesulphides is a relatively fast reaction and is due to the addition of the respective bisarenesulphide radical cation to bisarenesulphide molecules. The reason for the striking mechanistic difference for the two groups of radical cations is very likely an unfavourable disproportionation equilibrium for the more reaction bisarenesulphide radical cations.     

Selective oxidation of styrenes under oxygen catalyzed by cobalt chloride

The cobalt(II) chloride-catalyzed oxidative cleavage of -methylstyrene with oxygen in t-BuOH gives acetophenone and formaldehyde in good yield. The competing reactions between C=C cleavage and formation of polymeric products are strongly affected by the solvent, cobalt catalyst and concentration used, as well as the reaction temperature. A free radical mechanism involving a cyclic peroxide intermediate is proposed to give the cleavage products. Oxidation of various alkenes using CoCl₂/t-BuOH/O₂ system shows that only activated styrenes can be oxidized effectively. The reactivity of various styrenes and their selectivity towards giving cleavage products or polymers are strongly influenced by the electronic and steric properties of the substrate.     

ESR-Spektroskopischer nachweis von radikalkationen bei der anodischen oxidation von alkylbenzolen in methylenchlorid und trifluoressigsäure

The anodic oxidation of hexaethyl- (HEB), hexa-methyl- (HMB), pentamethyl- (PMB) and 1,2,4,5-tetramethyl-benzene (TMB) on Pt in CH₂Cl₂ and CF₃COOH (TFA) is examined by cyclic voltammetry and esr spectroscopy. HEB, HMB and PMB are oxidized to the corresponding radical cations in TFA. The anodic oxidation of HMB and PMB in CH₂Cl₂ results in radical cations with one methyl group more than the starting material. The mechanism of the formation of these radical cations is discussed for HMB.     

Spontaneous formation and transformation of organic free radical cations upon adsorption of olefins on H-mordenite

The radical cation of 2,5-dimethyl-2,4-hexadiene is identified by ESR upon adsorption of the parent molecule on activated H-mordenite. The same radical is observed when 2,3-dimethyl-1-butene or 2-methylpropene is adsorbed. This is clear evidence for highly specific dimerisation-fragmentation reactions of the primary radical cations in the zeolite at room temperature.     

Arylation reactions: the photo-S(N)1 path via phenyl cation as an alternative to metal catalysis

Photo(sensitized) cleavage of benzenediazonium salts as well as, when an electron-donating substituent is present, of aryl chlorides, fluorides, mesylates, triflates, and phosphates leads to the corresponding phenyl cations in the triplet state. These otherwise unavailable intermediates add selectively to alkenes, alkynes, and (hetero)arenes, giving arylation products in a good yield. The reactions are photochemical alternatives of metal-catalyzed Heck and cross-coupling reactions and bear some mechanistic analogy with them.     

Interaction of poly(methyl methacrylate) and nafions

The thermal degradation of Nafion–H, Nafion–K, and the mixture of each of these with poly(methyl methacrylate) (PMMA) has been studied. A mechanism is proposed for the thermal degradation of Nafion–H that involves an initial cleavage of the carbon–sulfur bond leading to SO₂ and OH radical and a carbon-based radical. This carbon-based radical then undergoes further degradation. The addition of PMMA to Nafion–H inhibits further degradation of the Nafion carbon-based radical and instead radical recombination reactions between PMMA fragments and this Nafion radical dominate the reaction scheme. The replacement of the hydrogen in Nafion–H with a potassium (i.e., Nafion–K) produces a much more robust material that does not degrade under conditions similar to those used for Nafion–H. Nafion–K has little effect on the degradation of PMMA.     

Reactions of Metal Ion Complexes with Lignin Model Compounds,Part II. Fe(TSPC) Catalyzed Formation of Oxidized Products in the Absence of Oxygen

The water soluble phthalocyanine complex trisodium tetra-4-sulfonatophthalocyanineiron(III) (Fe(TSPc)) was found to be an effective catalyst for the cleavage of the β-ether bonds in the phenolic lignin model compounds guaiacylglycol β-guaiacyl ether (1) and guaiacylglycerol β-guaiacyl ether (11). The products of these reactions were very different from those formed in the corresponding reactions catalyzed by anthraquinone (AQ) or Co(SPP).^1–4 In particular, they gave large quantities of oxidized products, even though the reactions were performed in the absence of oxygen or other added oxidant. Mechanisms have been proposed for the oxidation reactions involving 1 and 11. In both cases the first step involves one electron oxidation of the lignin model compound by the catalyst. The radical derived from 1 then undergoes further one electron oxidation and deprotonation to give 4′-hydroxy-3′-methoxy-l-(2″-methoxyphenoxy)acetophenone (8) whereas that derived from 11 undergoes Cα-Cβ bond cleavage to give vanillin (4). Reactions of the reduced form of the catalyst with 8 and the quinone methides produced from the phenolic models are important routes for guaiacol formation and regeneration of the oxidized form of the catalyst. The feasibility of these proposed reaction pathways was investigated by studying the reactions of the intermediate compounds with the catalyst.     

Zur Allyl-Cyclopropyl-Isomerie von substituierten Kationen: Eine AMl- und MNDO-Untersuchung

On the Allyl-Cyclopropyl Isomerism of Substituted Cations: An AMl and MNDO Study Three series of cations (2-X-allyl cations ( 1 ), 1-X-cyclopropyl cations ( 2 ) and 1-X-isopropyl cations ( 3 )) were investigated by both the MNDO and AMl quantum chemical methods. For π-electron donators (X = NH₂, OH, NHOH) derivatives 2 are more stable than 1 . The opposite is valid for derivatives with δ-electron acceptors (X = NO₂, CHO, halogens). AMl values are closer to experimental or ab initio heats of formation than MNDO results. Therefore, by means of AMl only, reasonable ringstrain energies were obtained for 2 , while the MNDO method failed in all investigated cases. It has been shown that the unknown 2-hydroxyaminoallyl cation is probably more stable than its cyclopropyl analogue.     

Non-heme Fe(IV)-oxo intermediates

High-valent non-heme iron-oxo intermediates have been proposed for decades as the key intermediates in numerous biological oxidation reactions. In the past three years, the first direct characterization of such intermediates has been provided by studies of several alphaKG-dependent oxygenases that catalyze either hydroxylation or halogenation of their substrates. In each case, the Fe(IV)-oxo intermediate is implicated in cleavage of the aliphatic C-H bond to initiate hydroxylation or halogenation. The observation of non-heme Fe(IV)-oxo intermediates and Fe(II)-containing product(s) complexes with almost identical spectroscopic parameters in the reactions of two distantly related alphaKG-dependent hydroxylases suggests that members of this subfamily follow a conserved mechanism for substrate hydroxylation. In contrast, for the alphaKG-dependent non-heme iron halogenase, CytC3, two distinct Fe(IV) complexes form and decay together, suggesting that they are in rapid equilibrium. The existence of two distinct conformers of the Fe site may be the key factor accounting for the divergence of the halogenase reaction from the more usual hydroxylation pathway after C-H bond cleavage. Distinct transformations catalyzed by other mononuclear non-heme enzymes are likely also to involve initial C-H bond cleavage by Fe(IV)-oxo complexes, followed by diverging reactivities of the resulting Fe(III)-hydroxo/substrate radical intermediates.     

Effect of Counter Cation on Alkaline Reaction of β-O-4-Type Substructure in Lignin

This study aimed to clarify the effects of counter cations on the alkaline-induced β-O-4 bond cleavage and further reactions of β-O-4-type substructures in lignin. For this purpose, a non-phenolic β-O-4-type lignin model compound, the erythro isomer of 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (veratrylglycerol-β-guaiacyl ether), was treated in a 100% water solution or an aqueous methanol, ethanol, or 1,4-dioxane solution containing LiOH, NaOH, or CsOH as an alkaline source at 150?°C. The rates of β-O-4 bond cleavage were in the order of CsOH?>?NaOH?>?LiOH in all solvents. This order can rationally be attributed to the strength of the interactions between HO^– and the counter cations. Because Cs⁺ has the lowest positive charge density among the counter cations and hence interacts with HO^– most weakly, HO^– can exert its reactivity most actively in the reactions using CsOH. We also discuss how the counter cations affect the profile of reaction products.     

Oxidative radical generation via nitrogen dioxide dimer conversions induced by amide groups of macromolecules

The features of initiation of free radical reactions in polymers by dimers of nitrogen dioxide are considered. The conversion of planar dimers into nitrosyl nitrate in the presence of amide groups of macromolecules has been revealed. Nitrosyl nitrate initiates radical reactions in oxidative primary process of electron transfer with formation of intermediate radical cations and nitric oxide. As a result of subsequent reactions, nitrogen‐containing radicals are produced. The dimer conversion has been exhibited by estimation of the oxyaminoxyl radical yield in characteristic reaction of p‐benzoquinone with nitrogen dioxide on addition of aromatic polyamide and polyvinylpyrrolidone to reacting system. The isomerization of planar dimers is efficient in their complexes with amide groups, as confirmed by ab initio calculations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The Application of 3-Amino-2H-Azirines as Amino Acid Equivalents

3-amino-2H-azirines undergo a number of ring opening reactions. The cleavage of the azirine-N(1), C(3) double bond leads thereby to synthons which can be considered as amino acid equivalents. The reaction of 3-amino-2H-azirines with carboxylic acids yields N-acyl amino acid amides, which can be converted by a selective amide cleavage to the corresponding N-acyl amino acids. 2-Oxazolin-5-ones are intermediates of this amide cleavage. This reaction sequence has been used for the extension of peptide chains as well as for a number of heterocycle syntheses. Likewise, the described synthesis of cyclic depsipeptides and lactones by direct amide cyclization proceeds via 2-oxazolin-5-one intermediates. The selective amide cleavage was also applied to a novel method for the resolution of enantiomeric amino acid derivatives.     

Electrochemistry of Organic Cations. VI. Investigations about the Cathodic Cleavage of Some Pyridinium and Triazolium Ions

The electrochemical reduction of some N-acylamino-, N-amino-, N-benzyl- and N-phenacyl-substituted pyridinium and triazolium ions is investigated in acetonitrile by voltammetric methods and potentiostatic electrolyses. The acylaminopyridinium ions 1 and the arylaminopyridinium ions 3 are cathodically cleaved into the pyridine derivative and the carboxylic amide or the aromatic amine. In the case of the 1-benzyl-4-acylaminotriazolium ions 5 the reductive formation of hydrogen from the acidic N-acylamino group is preferred and the corresponding ylide is formed, which reacts at more negative potential by splitting off the benzyl group. The reduction of the N-phenacylpyridinium ion 7d occurs with splitting off the phenacyl radical, which dimerizes to 1,2-dibenzoylethane in a good yield. In the case of N-benzyl- and N-p-cyanobenzylpyridinium ions the cathodic dimerization to the corresponding bisdihydropyridines was found, whereas the electrolysis of the N-nitrobenzylpyridinium ions occurs with cleavage of the N-substituent-bond, which is initiated by the primary formation of the nitrophenyl anion radical. It follows from electrogenerated chemiluminescence experiments that the cleavage of the cations 1 and 5 occurs with the uptake of one electron.     

Mechanisms of Oxidative Degradation of Carbohydrates During Oxygen Delignktcation. I. Reaction of Methyl β-D-Glucopyranoside with Photochemically Generated Hydroxyl Radicals

Abstract

Hydroxyl radical is considered to be the major species causing degradation of carbohydrates during oxygen delignification. In this study, reactions involving a carbohydrate model compound and either photochemically generated hydroxyl radical or superoxide from potassium superoxide were carried out to investigate the cleavage of glycosidic linkages. Experiments show that hydroxyl radicals are responsible for the degradation of glycosidic linkages in methyl β-D-glucopyranoside by a substitution reaction displacing D-glucose. Once the glycosidic linkage is broken, reducing carbohydrates undergo a series of reactions forming aldonic acids and lower order aldoses. Control experiments established that no reaction occurs in the absence of UV light under otherwise identical conditions.     

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.     

A radical ion-pair complex exhibiting strong C–H…O H-bonding interaction,moderately broaden near-IR absorbance and complicated EPR spectrum

An ion-pair complex of [Ni(mnt)₂]^2? with p-N-benzylpyridinium α-nitronyl nitroxide radical cations (p-BzPYNN) in acetonitrile shows a moderate and broad absorbance in near-IR region. In the crystal of this complex, two radical cations form a dimer via strong H-bonding interaction; such kinds of dimers are connected into H-bonding chain by [Ni(mnt)₂]^2? dianions through weak H-bonding interactions. The neighboring H-bonding chains are arranged into supramolecular sheet via π…π stacking interactions between the five-membered chelate-ring of anion and the superimposed pyridyl rings of cations. The polycrystalline EPR spectrum exhibits two isotropic EPR signals. Based on the analyses of crystal structure, variable temperature magnetic susceptibility and electronic spectrum, the stronger EPR signal is assigned to the radical cation, the weaker one probably arises from a trace amount of [Ni(mnt)₂]^1? species.     

Investigations on Structural and Electrochemical Properties of Some Disulfides Prepared by Schiff Base Reactions

Four different disulfides, [2,2′‐dithiobis‐(2‐mercaptoacetophenone)]‐4‐triphenylmethylthiosemicarbazone ( 1 ), [5,5′‐dithiobis‐(4‐formyl‐3‐methyl‐1‐phenylpyrazole)]‐4‐triphenylmethylthiosemicarbazone ( 2 ), bis[1‐(2‐mercaptophenyl)‐2‐(4‐(1‐phenyl‐3‐methyl)pyrazole)‐azaethene]di‐sulfide ( 3 ) and bis[1‐phenyl‐2‐(4‐(1‐phenyl‐3‐methyl‐5‐mercapto) pyrazole)‐azaethene]disulfide ( 4 ) were synthesized by Schiff base reactions. Their electrochemical behaviour was examined by cyclic voltammetry. The results show low potentials for the disulfide reduction so that these compounds are suitable for the syntheses of tridentate thiolate ligands from disulfides by electrochemical cleavage. In addition compounds 2 and 4 were characterized by X‐ray structure determination. The structures show significant differences of the S—S bonds and angles as compared to other disulfides without bulky substituents.