Spectroscopic and computational studies on the rearrangement of ionized [1.1.1]propellane and some of its valence isomers: the key role of vibronic coupling

The [1.1.1]propellane radical cation 1(?+), generated by radiolytic oxidation of the parent compound in argon and Freon matrices at low temperatures, undergoes a spontaneous rearrangement to form the distonic 1,1-dimethyleneallene (or 2-vinylideneallyl) radical cation 3(?+) consisting of an allyl radical substituted at the 2-position by a vinyl cation. In similar matrix studies, it is found that the isomeric dimethylenecyclopropane radical cation 2(?+) also rearranges to 3(?+). The unusual molecular and electronic structure of 3(?+) has been established by the results of ESR, UV-vis, and IR spectroscopic measurements in conjunction with detailed theoretical calculations. Also of particular interest is an NIR photoinduced reaction by which 3(?+) is cleanly converted to the vinylidenecyclopropane radical cation 4(?+), a process that can be represented in terms of a single electron transfer from the allyl radical to the vinyl cation followed by allyl cation cyclization. The specificity of this photochemical reaction provides additional strong chemical evidence for the structure of 3(?+). Theoretical calculations reveal the decisive role of vibronic coupling in shaping the potential energy surfaces on which the observed ring-opening reactions take place. Thus vibronic interaction in 1(?+) mixes the (2)A(1)' ground state, characterized by its "non-bonding" 3a(1)' SOMO, with the (2)E' first excited state resulting in the destabilization of a lateral C-C bond and the initial formation of the methylenebicyclobutyl radical cation 5(?+). The further rearrangement of 5(?+) to 3(?+) occurs via 2(?+) and proceeds through two additional lateral C-C bond cleavages characterized by transition states of extremely low energy, thereby explaining the absence of identifiable intermediates along the reaction pathway. In these consecutive ring-opening rearrangements, the "non-bonding" bridgehead C-C bond in 1(?+) is conserved and ultimately transformed into a normal bond characterized by a shorter C-C bond length. This work provides strong support for the Heilbronner-Wiberg interpretation of the vibrational structure in the photoelectron spectrum of 1 in terms of vibronic coupling.     

The isolable cation radical of disilene: synthesis, characterization, and a reversible one-electron redox system

The highly twisted tetrakis(di-tert-butylmethylsilyl)disilene 1 was treated with Ph3C+.BAr4- (BAr4-: TPFPB = tetrakis(pentafluorophenyl)borate) in toluene, producing disilene cation radical 3 upon one-electron oxidation. Cation radical 3 was isolated in the form of its borate salt as extremely air- and moisture-sensitive red-brown crystals. The molecular structure of 3 was established by X-ray crystallography, which showed a highly twisted structure (twisting angle of 64.9 degrees) along the central Si-Si bond with a bond length of 2.307(2) A, which is 2.1% elongated relative to that of 1. The cation radical is stabilized by sigma-pi hyperconjugation by the four tBu2MeSi groups attached to the two central sp2-Si atoms. An electron paramagnetic resonance (EPR) study of the hyperfine coupling constants (hfcc) of the 29Si nuclei indicates delocalization of the spin over the central two Si atoms. A reversible one-electron redox system between disilene, cation radical, and anion radical is also reported.     

Effects of structural factors on the pi-dimerization and/or disproportionation of the cation radical of extended TTF containing thiophene-based pi-conjugated spacers

The electrochemical and chemical oxidation of extended TTF 4 and 5 are analysed by cyclic voltammetry, Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5 x BF(4)(CH(2)Cl(2)) and 4 x ClO(4)(THF)(1/2) are presented. The effects of structural factors on the pi-dimerization or the disproportionation reaction of the cation radical are shown. The oxidation of compound 4 presents the successive formation of stable cation radical and dication species both in dichloromethane (DCM) and in a CH(3)CN/THF mixture. In contrast, for compound 5, the stability of the oxidation states strongly depends on the nature of the solvent. In DCM, the oxidation of 5 proceeds by two close one-electron transfers while in CH(3)CN/THF the dication is directly formed via a two-electron process. The X-ray structures of the two salts reveal the formation of pi-dimers of cation radical. While the dimer (5(2))(2+) is due mainly to pi-pi interactions between the conjugating spacer, the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and pi-pi interactions. Visible/NIR and ESR experiments confirm the higher tendency of 4(+)(.) to dimerize with the occurrence of dimer and monomer in solution, while for 5(+)(.) only the monomer is detected in DCM. On the other hand, by dissolution of 5 x BF(4)(CH(2)Cl(2)) in CH(3)CN, only the neutral and the dicationic states of compounds 5 are observed owing to the disproportionation reaction.     

Effects of protonation and metal coordination on intramolecular charge transfer of tetrathiafulvalene compound

A protonated bifunctional pyridine-based tetrathiafulvalene (TTF) derivative (DMT-TTF-pyH)NO3 and a copper(II) complex Cu(acac)2(DMT-TTF-py)2 have been obtained and studied. Electronic spectra of the protonated compound show a large ICT (intramolecular charge transfer) band shift (Deltalambda=136 nm) compared with that of the neutral compound. Cyclic voltammetry also shows a large shift of the redox potentials (DeltaE1/2(1)=77 mV). Theoretical calculation suggests that the pyridium substituent is a strong pi-electron acceptor. Crystal structures of the protonated compound and the metal complex have been obtained. The dihedral angle between least-squares planes of the pyridyl group and the dithiole ring might reflect the intensity of the ICT effect between the TTF moiety and the pyridyl group. It is also noteworthy that the TTF moiety could be oxidized to TTF2+ dication by Fe(ClO4)(3).6H2O when forming a metal complex, while the protonated TTF derivative can only be oxidized to the TTF*+ radical cation by Fe(ClO4)(3).6H2O even with an excess amount of the Fe(III) salt, which can be used to control the oxidation process to obtain neutral TTF, TTF*+ radical cation, or TTF2+ dication.     

Pulse Radiolytic Studies of 1-Halo-2-(methylthio)ethanes in Hexane and 1,2-Dichloroethane: Formation of an Intermolecular Species with a Three-Electron Bond between Sulfur and Iodine

1-Iodo-2-(methylthio)ethane was synthesized via a ring-opening reaction of thiirane with MeI in MeCN. The S-centered radical cation of this compound undergoes an intermolecular stabilization with the I substituent of a second unattacked substrate molecule to yield an bonded radical cation. The oxidation was initiated by solvent radical cations in irradiated 1,2-dicloroethane and hexane solutions. The 2ρ/ρ* three-electron-bonded species exhibits an optical absorption band at 410 nm, detectable by pulse radiolysis. During its decay, a new, longer-lived absorption band is formed at 380 nm which is assigned to . The latter is suggested to result from anchimeric assistance in the generation of a cyclic sulfonium salt. The radical cations of 1-bromo-and 1-chloro-2-(methylthio)ethane are assumed to undergo raped cyclization to the sulfonium salt without stabilization in any intermolecular S-Br or S-Cl interaction.     

Steric effects on the reversible dimerization of short-chain oligothiophene cation radicals

The reversible dimerization of cation radicals of a series of end-capped 2,5″-dihexylterthiophenes with the median thiophene ring either unsubstituted (1) or mono- and di-substituted by methyl and hexyl groups (2–5) has been investigated. Concentration-dependent cyclic voltammetry, UV-Vis-NIR spectroelectrochemistry and temperature-dependent ESR spectroscopy lead to consistent results showing that, whereas the cation radical of compound 1 already dimerizes at room temperature, substitution of the median thiophene ring leads to a dramatic decrease in the propensity of the corresponding cation radical to dimerize. These results provide conclusive evidence for a steric control of the reversible dimerization of short-chain oligothiophene cation radicals.     

Electrochemical Production and Examination of Redox Conversions of 2,4-Diphenyl-6H-cyclopenta[b]thiopyran and 2,4-Diphenylcyclopenta[b]thiopyrilium Perchlorate

The mechanism governing the formation of 2,4-diphenyl-6H-cyclopenta[b]thiopyran and corresponding thiopyrilium perchlorate from 1,3-diphenyl-3-(2-oxocyclopentyl)-1-propanon in conditions of oxidative activation of hydrogen sulfide is considered. The process of oxidation of 2,4-diphenyl-6H-cyclopenta[b]thiopyran in a nonaqueous environment is shown to proceed stepwise through the intermediate formation of a radical cation, radical, and anhydrobase, to aromatic system 2,4-diphenylcyclopentadieno[b]thiopyranilidene. A similar product is obtained when oxidizing the 2,4-diphenylcyclopenta[b]thiopyrilium cation. Reduction of thiopyrilium perchlorate was observed to lead to the formation of a 2,4-diphenylcyclopenta[b]thiopyranyl radical, which is confirmed by an ESR method. The mechanism of redox conversions of thiopyran and thiopyrilium salt is substantiated by a quantum-chemical calculation.     

Immobilization of Glycosylated Enzymes on Carbon Electrodes,and its Application in Biosensors

A novel approach was used to immobilize glycosylated enzymes on a glassy carbon electrode (GCE) based on the interaction of boronic acid and carbohydrate moiety within the glycoproteins. 4-Aminomethylphenylboronic acid (4-AMBA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. The boronic acid group immobilized in this way could recognize glycoproteins such as glucose oxidase, horseradish peroxidase, dehydrogenase and others. X-ray photoelectron spectroscopy measurement proved the presence of a 4-AMBA monolayer on the GCE. The adsorptions of three kinds of enzymes were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The activity of the immobilized horseradish peroxidase was also studied.     

Structure,Physicochemical and Biological Properties of an Aqua (2,2′,2′′‐Nitrilotriacetato)‐oxidovanadium(IV) Salt with 4‐Methylpyridinium Cation

The crystal structure of a nitrilotriacetate (nta) oxidovanadium(IV) salt with 4‐methylpyridinium cation, [4‐Me(Py)H]⁺, of [4‐Me(Py)H][VO(nta)(H₂O)] stoichiometry was determined. The complex comprises a discrete mononuclear [VO(nta)(H₂O)]^– coordination entity that can be rarely found among other known compounds containing nitrilotriacetate oxidovanadium(IV) moieties. The complex was characterized by spectroscopic (IR and EPR) methods, magnetic measurements, and thermogravimetry (TG‐FTIR). The stability of the title compound in aqueous solutions was investigated by using the potentiometric titration method. Furthermore, spectrophotometric (UV/Vis) studies have revealed that the compound is capable to scavenge the superoxide free radicals (O₂ ^{? –}) as well as stable organic radicals i.e. 2,2′‐azinobis(3‐ethylbenzothiazoline‐6 sulfonic acid) cation radical (ABTS^{+ ?} ) and 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH ^? ). Finally, biological properties of the complex studied were investigated in relation to its cytoprotective activity against the oxidative damage generated exogenously by using hydrogen peroxide in the HT22 hippocampal neuronal cell line (the MTT assay). Additionally, the biological action of the compound towards two human osteosarcoma HOS and MG‐63 cell lines (the MTT and BrdU tests) as well as the untransformed human osteoblast hFOB 1.19 cell line was tested.     

The stable radical cation of thiophene annelated with bicyclo[2.2.2]octene and its reaction with triplet oxygen to give a protonated cation of 2-butene-1,4-dione derivative

The first isolable salt of the thiophene radical cation was prepared from the derivative annelated with two bicyclo[2.2.2]octene units, and its reaction with triplet oxygen was found to give a novel cation of a proton-chelating 2-butene-1,4-dione derivative with remarkable stability.     

Reactivity of the 4,5-didehydroisoquinolinium cation

The chemical properties of a 1,8-didehydronaphthalene derivative, the 4,5-didehydroisoquinolinium cation, were examined in the gas phase in a dual-cell Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer. This is an interesting biradical because it has two radical sites in close proximity, yet their coupling is very weak. In fact, the biradical is calculated to have approximately degenerate singlet and triplet states. This biradical was found to exclusively undergo radical reactions, as opposed to other related biradicals with nearby radical sites. The first bond formation occurs at the radical site in the 4-position, followed by that in the 5-position. The proximity of the radical sites leads to reactions that have not been observed for related mono- or biradicals. Interestingly, some ortho-benzynes have been found to yield similar products. Since ortho-benzynes do not react via radical mechanisms, these products must be especially favorable thermodynamically.     

Radical/cation transformation polymerization and its application to the preparation of block copolymers

p-Methoxystyrene (MOS), butyl vinyl ether (BVE), and N-vinylcarbazole (VCZ) were polymerized in high yield by azoinitiators such as 2, 2'-azodiisobutyronitrile (AIBN) in the presence of electron acceptors such as Ph₂I⁺PF₆⁻. An electron paramagnetic resonance (ESR) study of the model radicals of the propagating radical showed the transformation of the radical to the corresponding cation in the presence of the electron acceptors. In the case of BVE, the polymer formation was caused by cationic species produced by the transformation of the initiating radical. The polymerizations of MOS and VCZ were ascribed to the transformation of the growing radical to the corresponding cation during the propagation step which was classified as the radical/cation transformation polymerization. Block copolymers of MOS/cyclohexene oxide (1, 2-epoxycyclohexane) (CHO) and VCZ/CHO were effectively prepared by the radical/cation transformation polymerization of the appropriate monomers in the presence of AIBN, electron acceptor and CHO. The formation of block copolymers was characterized by turbidimetry, thin-layer chromatography, and solubility tests.     

Effect of cation size and charge on the interaction between silica surfaces in 1:1, 2:1, and 3:1 aqueous electrolytes

Application of two complementary AFM measurements, force vs separation and adhesion force, reveals the combined effects of cation size and charge (valency) on the interaction between silica surfaces in three 1:1, three 2:1, and three 3:1 metal chloride aqueous solutions of different concentrations. The interaction between the silica surfaces in 1:1 and 2:1 salt solutions is fully accounted for by ion-independent van der Waals (vdW) attraction and electric double-layer repulsion modified by cation specific adsorption to the silica surfaces. The deduced ranking of mono- and divalent cation adsorption capacity (adsorbability) to silica, Mg(2+) < Ca(2+) < Na(+) < Sr(2+) < K(+) < Cs(+), follows cation bare size as well as cation solvation energy but does not correlate with hydrated ionic radius or with volume or surface ionic charge density. In the presence of 3:1 salts, the coarse phenomenology of the force between the silica surfaces as a function of salt concentration resembles that in 1:1 and 2:1 electrolytes. Nevertheless, two fundamental differences should be noticed. First, the attraction between the silica surfaces is too large to be attributed solely to vdW force, hence implying an additional attraction mechanism or gross modification of the conventional vdW attraction. Second, neutralization of the silica surfaces occurs at trivalent cation concentrations that are 3 orders of magnitude smaller than those characterizing surface neutralization by mono- and divalent cations. Consequently, when trivalent cations are added to our cation adsorbability series the correlation with bare ion size breaks down abruptly. The strong adsorbability of trivalent cations to silica contrasts straightforward expectations based on ranking of the cationic solvation energies, thus suggesting a different adsorption mechanism which is inoperative or weak for mono- and divalent cations.     

Radical cations from dicyclopropylidenemethane and its octamethyl derivative

The radical cations of dicyclopropylidenemethane (2) and its octamethyl derivative (2-Me8) are prone to rearrangements into those of (2-methylallylidene)cyclopropane (2a) and its octamethyl derivative (2a-Me8), respectively, by opening one three-membered ring. In contrast to the radical cations of bicyclopropylidene (1) and its octamethyl derivative (1-Me8), 2*+ and 2-Me8*+ are stable to opening of the second ring, because in this case the resulting species would be a non-Kekulé hydrocarbon with a quartet ground state. Similarly to 1, octamethyl substitution in 2 promotes the tendency to rearrangement. Thus, ESR and ENDOR studies indicate that the primary radical cation 2*+, which is formed upon gamma-irradiation of 2 in a CFCl3 matrix at 77 K, does not rearrange up to 150 K. On the other hand, when 2-Me8 is treated in the same way, only the rearranged radical cation 2a-Me8*+ can be observed and characterized by its ESR and ENDOR spectra. Nevertheless, the existence of the two "missing" species, 2a*+ and 2-Me8*+, is revealed by other methods. According to UV and IR studies, X irradiation of 2 in an Ar matrix leads directly to the ring-opened radical cation 2a*+. Moreover, magnetic field effects on the decay of fluorescence, which appears upon recombination of the radical anion of p-terphenyl with a radical cation generated from 2-Me8 in liquid octane, strongly suggest that 2-Me8*+ (and not 2a-Me8*+) is formed initially. From the temperature dependence of the decay, the activation energy of the ring-opening process 2-Me8*+ --> 2a-Me8*+ is estimated. The radical cations 2a*+ and 2a-Me8*+ are formally distonic with the spin residing in the allylic moiety and the charge accommodated on the central carbon atom of the allene pi-system. The intact cyclopropylidenemethylidene moiety assumes a "bisected" conformation, thus favoring an optimal interaction with the positively charged center on the pi-system.     

Low‐Temperature Isolation of the Bicyclic Phosphinophosphonium Salt [Mes*2P4Cl][GaCl4]

The reaction of [ClP(μ‐PMes*)]₂ ( 1 ) with the Lewis acid GaCl₃ yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan‐2‐ium salt, [Mes*P₄(Cl)Mes*][GaCl₄] ( 3 [GaCl₄]), which incorporates a positively charged phosphonium center within its bicyclic P₄ scaffold. The formation of the title compound was studied by means of low‐temperature NMR experiments. This led to the identification of an intermediate cyclotetraphosphenium cation, which was trapped by reaction with dimethylbutadiene (dmb). All of the compounds were fully characterized by experimental and computational methods.     

Novel cation [N(SO2NMe3)2]+ and its synthesis and crystal structure. Dichloride of imido-bis(sulfuric) acid HN(SO2Cl)2. Part 1. Crystal structures of KN(SO2Cl)2.(1/2)CH3CN, KN(SO2Cl)2.(1/6)CH2Cl2, and [PCl4][N(SO2Cl)2

Several salts of bis(chlorosulfonyl)imide HN(SO2Cl)2 (1), namely, two solvates of its potassium salt, KN(SO2Cl)2.(1/2)CH3CN (1K1), KN(SO2Cl)2.(1/6)CH2Cl2 (1K2), and its tetrachlorophosphonium salt, [PCl4][N(SO2Cl)2] (2), were prepared and structurally characterized. The reaction of HN(SO2Cl)2 with Me3N gives the [N(SO2Cl)2]- salt of a novel cation, [N(SO2NMe3)2]+. This cation is analogous to the [HC(SO2NMe3)2]+ cation, but in contrast to the latter, it is fairly stable to hydrolysis. The salt [N(SO2NMe3)2]+[N(SO2Cl)2]- (3) can be converted into salts of other anions by being treated with diluted aqueous solutions of the respective acids, and thus NO3-, Cl-.H2O, SeO3(2-), CH3COO-, HSO4-, (COO)2(2-) salts were prepared. Treatment of 3 with concentrated HNO3 gave the [N(SO2NMe3)2]+ [O2NO-H-ONO2]- salt, and the addition of an HCl-acidified FeCl3 aqueous solution yielded the FeCl4- salt. Methanolysis resulted in the formation of MeOSO3- and [MeOSO2NSO2OMe]- salts. All salts have been characterized by chemical analysis, vibrational spectroscopy, and X-ray structure determinations.     

Unexpected Hofmann elimination in the benzophenone-(phenylthio)acetic tetrabutylammonium salt photoredox system

The triplet state of benzophenone was quenched by the tetrabutylammonium salt of (phenylthio)acetic acid in acetonitrile solutions. The quenching event, following laser flash photolysis, resulted in the formation of a transient ion pair consisting of the benzophenone radical anion and the tetrabutylammonium cation. Subsequently this ion pair decays with the quaternary ammonium cation undergoing a Hofmann elimination to form butane-1 and tributylamine, which were detected in steady-state irradiation. This appears to be the first report of an ion pair consisting of a benzophenone radical anion and an organic cation (nonradical), in addition to the first report of a photoinduced Hofmann elimination in quaternary ammonium ions.     

Anodic electrodeposition of NiTSPP from aqueous basic media

The oxidative electrodeposition of NiTSPP (tetrakis(4-sulfonatophenyl) Ni porphyrin) on ITO electrode from 0.1 M NaOH aqueous solution has been studied, and UV-visible and reflection FTIR spectroscopies have been used to analyze the composition of such film. By use of UV-vis spectroscopy, small absorbance of the film and an almost nulling effect on the Soret band of the porphyrin along the Ni(III)/Ni(II) redox process were observed. The reflection FTIR spectroscopy detected the presence of Ni-OH groups in the reduced film and as well the state of the porphyrin molecules as radical cation. Moreover, the porphyrin has been quantified by means of the area of the vibration bands assigned to the sulfonate groups by using as reference a Langmuir-Blodgett film containing a known surface concentration of NiTSPP. These results lead us propose the formation of a conductor salt by electrocrystallization, with stoichiometries TSPP/Ni(II)(OH)2 and TSPP/Ni(III)OOH, for its reduced and oxidized forms, respectively. In these two forms, the porphyrin rings will be present as radical cation, which may be stabilized through its dimerization or polymerization.     

Electron transfer between protonated and unprotonated phenoxyl radicals

The reaction of phenoxyl radicals with acids is investigated. 2,4,6-Tri-tert-butylphenoxyl radical (13), a persistent radical, deteriorates in MeOH/PhH in the presence of an acid yielding 4-methoxycyclohexa-2,5-dienone 18a and the parent phenol (14). The reaction is facilitated by a strong acid. Treatment of 2,6-di-tert-butyl-4-methylphenoxyl radical (2), a short-lived radical, generated by dissociation of its dimer, with an acid in MeOH provides 4-methoxycyclohexa-2,5-dienone 4 and the products from disproportionation of 2 including the parent phenol (3). A strong acid in a high concentration favors the formation of 4 while the yield of 3 is always kept high. Oxidation of the parent phenol (33) with PbO(2) to generate transient 2,6-di-tert-butylphenoxyl radical (35) in AcOH/H(2)O containing an added acid provides eventually p-benzoquinone 39 and 4,4'-diphenoquinone 42, the product from dimerization of 35. A strong acid in a high concentration favors the formation of 39. These results suggest that a phenoxyl radical is protonated by an acid and electron transfer takes place from another phenoxyl radical to the protonated phenoxyl radical, thus generating the phenoxyl cation, which can add an oxygen nucleophile, and the phenol (eq 5). The electron transfer is a fast reaction.     

The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines

The regioselectivity of the nitrous acid mediated dealkylation of 4-substituted-N-ethyl-N-methylanilines is a function of the acidity of the reaction mixture. At high acidity deethylation predominates, whereas demethylation is the predominant reaction in nitrosamine formation at pH 2 and above. In some cases the regioselectivity of nitrosative dealkylation changes as the run proceeds. Through the use of the corresponding 4-nitroaniline as the primary substrate, CIDNP, kinetics, kinetic deuterium isotope effects and other transformations involving nitrosations with NO2 or NOBF4 in aprotic solvents, a new mechanism of tertiary amine nitrosation has been deduced and proposed to explain regioselective deethylation. The mechanism involves the oxidation of the substrate to the amine radical cation by NO+. This is followed by the abstraction of a hydrogen atom from the carbon adjacent to the amine nitrogen by NO2 to produce an iminium ion which reacts further to produce the corresponding aldehyde and the nitrosamine. Depending upon the acidity, this process competes with three other mechanistic pathways, two of which give the nitrosamine through the iminium ion, and one leads to the formation of C-nitro compounds. The competing pathways to nitrosamine formation involve NOH elimination from a nitrosammonium ion and deprotonation of the radical cation to give an alpha-amino radical which rapidly oxidized to the iminium ion. Predominant, but not highly regioselective demethylation occurs by these pathways. Nitro compound formation principally arises from the reaction of NO2 with the radical cation followed by deprotonation, but also occurs by para C-nitrosation followed by oxidation.