Reactions of phenylium ions with gaseous hydrocarbons. 1. methane,ethane, and propane

The reaction of free tritiated phenylium ion, generated from nuclear decay of [l,4-T₂]-benzene in the presence of simple gaseous hydrocarbons RH (R = CH₃, C₂H₅, C₃H₇; partial pressure: 10-100 torr), yields predominantly the corresponding tritiated C₆H₅R products. The effects of gaseous nucleophilic acceptors (NuH = NH₃, CH₃OH) on the reaction with CH₄, were also investigated. Phenylium ion confirms its exceedingly high reactivity even toward pure σ- -type substrates, as well as its considerable site selectivity, demonstrated by the distinct preference for the C-H bonds of the substrate. The stability features of the ionic intermediates from addition of phenylium ion with RH have been evaluated, as well as their fragmentation and isomerization mechanisms. The behaviour of phenylium ion toward simple aliphatic hydrocarbons in the gas phase (10-100 torr) is discussed and compared with previous mechanistic hypotheses from ICR mass spectrometric studies, carried out at much lower pressures (10^-5 torr).     

Site Selectivity in the Gas-Phase Ionic Phenylation of Alcohols and Alkyl Chlorides

Free, unsolvated phenylium ions formed by the spontaneous β decay of [1,4-³H₂]benzene have been allowed to react with gaseous alcohols (ROH: R = Et, CF₃CH₂, Pr, or i-Pr; partial pressure: 3–56 Torr) and alkyl chlorides (R′Cl: R′ = Pr, i-Pr, or Bu; partial pressure: 20–450 Torr), in the presence of a thermal radical scavenger (O₂: 4 Torr). Phenylium ion confirms its considerable site selectivity, demonstrated by the distinct preference toward the n-centre of the substrate (46–100%), although significant insertion into the alkyl group of alcohols is observed as well. Phenylium ion displays significant positional selectivity even between different n-type sites in a bidentate molecule such as CF₃CH₂OH. An affinity F < O < Cl trend is observed, which indicates a direct relationship between the polarizability of the n-centre of the molecule and its orienting properties toward phenylium ion. The stability features of the ionic intermediates from addition of phenylium ion with ROH or R′Cl have been evaluated, as well as their fragmentation and isomerization mechanisms. The behaviour of phenylium ion toward the selected substrates in the gas phase is discussed and compared with previous mechanistic hypotheses from related nuclear-decay studies.     

Substrate and Positional Selectivity of Free Phenylium Ions toward Arenes in the Gas and Liquid Phases

A nuclear technique, based on the spontaneous decay of tritiated precursors that allows the generation of free carbenium ion of exactly the same nature in different environments, has been exploited in a comparative study of aromatic phenylation by free phenylium ions, both in the gas phase at various pressures and in the liquid phase. The differences between the reactivity pattern of the phenylium ion in the two environments can essentially be reduced to significant ion-neutral electrostatic interaction in the gas phase and, to the much greater efficiency of collisional stabilization, in the condensed phase, allowing a larger fraction of the excited ionic intermediates, from the highly exothermic attack of phenylium ion on the competing arenes, to survive dissociation and isomerization. The mechanism of the major competitive processes promoted by phenylium-ion attack on arenes, i.e. phenyldehydrogenation and phenyldephenylation, are discussed, together with the substrate and positional selectivity displayed by the nuclear-decay-formed phenylium ion toward the selected arenes. The kinetic and mechanistic features of aromatic phenylation, deduced from the present decay experiments, are compared with those of related phenylation reactions carried out in the dilute gas state and in solution.     

First evidence for automerization of gaseous phenylium ion.

Tritium atom distribution in the anisole formed from the attack of a nucleogenic tritiated phenylium ion on gaseous methanol provides the first experimental evidence for a gas-phase automerization of phenylium ion.     

Charge stripping mass spectra: A method for identifying isomeric [C5H8]+˙ and [C3H6]+˙ ions

Charge stripping (collisional ionization) mass spectra are reported for isomeric [C₅H₈]⁺˙ and [C₃H₆]⁺˙ ions. The results provide the first method for adequately quantitatively determining the structures and abundances of these species when they are generated as daughter ions. Thus, loss of H₂O from the molecular ions of cyclopentanol and pentanal is shown to produce mixtures of ionized penta-1,3- and -1,4-dienes. Pent-1-en-3-ol generates [penta-1,3-diene]⁺˙. [C₃H₆]⁺˙ ions from ionized butane, methylpropane and 2-methylpropan-1-ol are shown to have the [propene]⁺˙ structure, whereas [cyclopropane]⁺˙ is produced from ionized tetrahydrofuran, penta-1,3-diene and pent-1-yne.     

Metastable ion studies. XII—Molecular and fragment ion structures for isomeric C4H6O2 acids

Metastable peak characteristics, ionization and appearance energy data and isotopic labelling experiments have been applied to a study of the fragmentation behaviour of the molecular ions of the isomeric C₄H₆O₂C acids, cis and trans-crotonic acids, methacrylic acid, butenoic acid and cyclopropane carboxylic acid. Prior to the losses of H₂O and CH₃, all the metastable molecular ions rearrange to [cis-crotonic acid]⁺? ions. Loss of H₂O, which generates a composite metastable peak, is proposed to yield vinylketene and/or cyclobutenone molecular ions. Detailed mechanisms are presented for the isomerizations of the various molecular ions and for the above fragmentations. Ionized 3-butenoic and cyclopropane carboxylic acids display a major loss of CO from their metastable ions, a minor process in the other isomers. The metastable peaks consist of two components and these are ascribed to the formation of propen-1-ol and allyl alcohol as daughter ions. Some comparative data are presented for the isomeric C₅H₈O₂ acids, tiglic acid, angelic acid and senecioic acid.     

Application of semiempirical MO calculations to the interaction of hydrocarbons with zeolites

In order to support previous spectral studies and normal coordinate analysis data, the semiempirical SCC-Xα method has been applied to the interaction of propene and cyclopropane with Ca²⁺ ions in front of the sixford windows connecting the sodalite units and the supercages in faujasites and A-type zeolites. From preliminary results, the ion can be approached by propene in a geometry intermediate between parallel or perpendicular orientation of its molecular plane normal to the double bond, while in case of cyclopropane an edge-on interaction seems to be favoured.     

Reaction from isomeric parent ions in the dissociation of dimethylpyrroles

The major dissociation pathways of the [M-H]⁺ (loss of NH₃ or CH₄) and the [M+H]⁺ (loss of NH₃ or CH₃) ions from dimethylpyrroles have been determined to occur from isomeric parent ions. For the [M-H]⁺ ion (formed by loss of a methyl hydrogen), loss of NH₃ leads to the formation of the phenylium ion and is preceded by consecutive carbon ring expansions followed by a ring contraction to form protonated aniline. Loss of CH₄ occurs after the first carbon ring expansion, which forms protonated picoline. The relative partitioning between the two dissociation paths depends upon the internal energy content of the parent ion; the highest point on the potential energy surface is the second ring expansion step. The [M+H]⁺ ion reacts through a similar pathway via dihydro analogs of picoline and aniline. The proposed reaction pathways are supported by results of semiempirical molecular orbital calculations.     

A comparison between gas phase simulated radiolysis with low energy electrons and mercury (3P1) photosentisized dissociation: chemical effects associated with the triplet states of propene

Results on the chemical effects associated with the three known triplet states of propene at 4.4, ≈6.1 and 7.7 eV, deduced from gas phase simulated radiolysis of propene and of its isomer cyclopropane with low energy electrons, are discussed. Data of previous authors on mercury authors on mercury (³P₁) photosensitized decomposition of propene are included in the discussion.     

Structures of decomposing and non-decomposing gas-phase [C4H6O]+· radical cations,and their [C2H2O]+· and [C3H6]+· product ions

The structures of gas-phase [C₄H₆O]^+· radical cations and their daughter ions of composition [C₂H₂O]^+· and [C₃H₆]^+· were investigated by using collisionally activated dissociation, metastable ion measurement, kinetic energy release and collisional ionization tandem mass spectrometric techniques. Electron ionization (70 eV) of ethoxyacetylene, methyl vinyl ketone, crotonaldehyde and 1-methoxyallene yields stable [C₄H₆O]^+· ions, whereas the cyclic C₄H₆O compounds undergo ring opening to stable distonic ions. The structures of [C₂H₃O]^+· ions produced by 70-eV ionization of several C₄H₆O compounds are identical with that of the ketene radical cation. The [C₃H₆]^+· ions generated from crotonaldehyde, methacrylaldehyde, and cyclopropanecarboxaldehyde have structures similar to that of the propene radical cations, whereas those ions generated from the remainder of the [C₄H₆O]^+· ions studied here produced a mixed population of cyclopropane and propene radical cations.     

A study of gaseous 3-membered ring oxonium and sulphonium ions

The 1-methyl-1-thionia cyclopropane 3 and 1-phenyl-1-thionia cyclopropane 4 ions are stable, with lifetimes greater than 10^?5 sec, and can be identified from their collisional activation spectra. Their metastable counterparts (lifetime window 10^?6–10^?5 sec) have undergone ring opening to the isomeric structures CH₃S⁺CHCH₃9 and C₆H₅S⁺CHCH₃11 prior to decomposition. The 1-methyl-1-oxonia cyclopropane 1 and 1-phenyl-1-oxonia cyclopropane 2 ions could not be generated: instead acyclic structures CH₃O⁺CHCH₃5 and C₆H₅O⁺CHCH₃7 were found for both metastable and long living species. Loss of a phenoxy radical from C₆H₅OCH₂CH₂OCH₃ is shown to be preceded by a reciprocal hydrogen transfer and is not due to a SN_i-type reaction.     

Reactions of the phenylium cation with small oxygen- and nitrogen-containing molecules

The reactions of phenylium with water and ammonia and their methyl homologs have been investigated using a quadrupole ion trap and semiempirical molecular orbital calculations. The results indicate that both types of molecules react with phenylium through lone pair electrons even though, for methyl-containing compounds, insertion into a C-H bond would lead to more stable products. For the excited adducts formed by reaction with methyl-containing reactant neutrals, the only dissociation observed is loss of a methyl radical. Neutral losses of H₂ or CH₄, which are more thermodynamically stable, are not observed, which indicates that these reactions are either not kinetically competitive or have high energy transition states due to the fact that the reactions would need to occur via orbital symmetry forbidden 1,2 eliminations.     

Electron-impact-induced rearrangements of organic ions VIUnimolecular reactions of isomeric[C8H9]+ions

Metastable ion spectra and deuterium labelling have been used to investigate a series of gaseous [C₈H₉]+ ions of isomeric structures. The similarity of the intensities of their metastable loss of hydrogen, acetylene and ethylene molecules and metastable reactions of specifically labelled ions, suggests that the [C₈H₉]+ reacting ions, formed initially with different structures, isomerise to a common structure or mixture of structures via deep-seated rearrangement reactions which render all hydrogen atoms equivalent. The isomerisation process involved is controlled by a conversion of a vinyl bond into an allyl-type bond, thus destroying the aromatic moiety.     

Formation and structure of [C8H8O]+˙ ions,generated from gas phase ions of phenyl-cyclopropylcarbinol and 1-phenyl-1-(hydroxymethyl)cyclopropane

The structure and formation of [C₈H₈O]^+. ions generated from phenylcyclopropylcarbinol and 1-phenyl-1-hydroxymethylcyclopropane upon electron impact, have been studied using kinetic energy release measurements, by determination of ionization and appearance energies and by collisional activation. It is shown that the non-decomposing [C₈H₈O]^+˙ ions have exclusively the structure of the enol ion of phenylacetaldehyde, although it is less stable than the enol ion of acetophenone by about 45 kJ mol^?1. This has been interpreted as an indication that the [C₈H₈O]^+˙ ions from phenylcyclopropylcarbinol are formed by an attack of either the phenyl ring or the hydroxyl group upon the C-1? C-2 (or C-1? C-3) bond of the cyclopropane ring under a simultaneous expulsion of ethene and migration of the attacking group to the C-1 position. The [C₈H₈O]^+˙ ion from 1-phenyl-1-(hydroxymethyl)cyclopropane is formed by opening of the cyclopropane ring via a benzylic cleavage. A kinetically controlled hydrogen shift in the resulting ring opened ion prior to or during ethene loss then leads to the formation of [C₈H₈O]^+˙ ions which have the structure of the enol ion of phenylacetaldehyde.     

Stoichiometric hydrogenation of the heterobimetallic (α-alkynyl) complex [μ(1σ, 23η3H2CC  CCH3)] [(CO)3FeCo(CO)3]

The title compound reacts with molecular hydrogen at 60°C giving rise to the homometallic complexes Fe(CO)₅ and Co₂(CO)₈, and a very rich mixture of gaseous hydrocarbons (e.g. butenes from partial hydrogenation, butane from total hydrogenation and methane and propene from selective hydrogenolysis of the organic chain).The influence of concentration of the title complex, and partial pressure of hydrogen or carbon monoxide on the hydrogenation rate have been investigated. Although an unequivocal mechanism cannot be ascertained from the kinetic data owing to the complexity of the reaction, the pattern of products strongly indicates that the σ-interaction between the iron atom and the organic chain is preserved in the transition state.     

Dimerization of Dimethyl 2‐(Naphthalen‐1‐yl)cyclopropane‐1,1‐dicarboxylate in the Presence of GaCl3 to [3+2], [3+3], [3+4], and Spiroannulation Products

In the presence of a catalytic amount of GaCl₃, dimethyl 2‐(naphthalen‐1‐yl)cyclopropane‐1,1‐dicarboxylate 5 undergoes selective [3+2]‐annulation‐type dimerization to give a polysubstituted cyclopentane containing two naphthalenyl substituents in the vicinal position (Scheme 2). Treatment of the same cyclopropane with an equimolar amount of GaCl₃?THF results in dimerization with electrophilic attack on each of the benzene rings to give [3+3] and [3+4] annulation products. The latter represent a new type of dimerization of donor? acceptor cyclopropanes. Finally, under conditions of double catalysis with GaCl₃, 3,3,5,5‐tetrasubstituted 4,5‐dihydropyrazole, this cyclopropane‐dicarboxylate undergoes stereospecific dimerization as a result of electrophilic ipso‐attack to give a tetracyclic pentaleno[6a,1‐a]naphthalene derivative (Scheme 5). Possible reaction mechanisms are proposed.     

The photolysis of platinacycloalkanes in solution

The photolysis of [I₂$\text{PtCH}{}_2\text{CH}{}_2\text{CH}{}_2\text{C}$H₂ (PMe₂ Ph)₂] gives ethylene and but-1-ene as volatile products, the latter probably being formed via a five-coordinate platinum intermediate. However, the formation of propene from the photolysis of [Cl₂$\text{PtCH}{}_2\text{CH}{}_2\text{C}$H₂ (1,10-phenanthroline) appears to involve a direct transfer of a hydrogen atom between neighbouring CH₂ groups in the ring. Other gaseous products, e.g. cyclopropane, ethylene, may be formed via a platinum ion radical.     

The photodecomposition of platinacycloalkanes in solution.: I. 1,3-propanediylplatinum(IV) compounds

The gaseous products of the photolysis at 25°C of the platinacyclobutane compounds [X₂$\text{PtCH}{}_2\text{CH}{}_2\text{C}$H₂(N-N)] where X = Cl, Br and N-N = 1,10-phenanthroline, 2,2′-bipyridine, (CH₂NMe₂)₂, (C₅H₅N)₂ in several solvents, in the absence and presence of various additives, have been determined. With solvents of relatively low dielectric constant (e.g. CH₂Cl₂), over 85 mol % of the hydrocarbon products was propene, the formation of which appears to involve a direct transfer of a hydrogen atom between neighbouring groups in the ring. With solvents of relatively high dielectric constant (MeCN, Me₂SO) in the presence of species, e.g. I^?, SbPh₃, having a high trans effect, cyclopropane is the main volatile product. The effect of added halide ion and of the mixed solvents Me₂SO/PhMe and Me₂SO/PhSH indicates that ionisation of the platinacyclobutane and the formation of platinum substituted propyl ion-radicals precede the formation of cyclopropane (and the small amounts of ethylene produced).The photolysis of [X₂$\text{PtCH}{}_2\text{CH}{}_2\text{C}$H₂(MeCN)₂] in methyl cyanide solution in the presence of Et₃RNX′ (X′ = Cl, R = H; X′ = Br, R = Et) gives appreciable amounts of ethylene in the products (up to 25 mol %). It is suggested that the halide ions add to the platinum to give negatively charged platinacyclobutane species, the photodecomposition of which may give C₂H₄.     

Some stereochemical effects in gaseous ion decompositions

Stereochemical effects were observed in the electron ionization, methane, isobutane and ammonia positive ion chemical ionization and hydroxy negative ion chemical ionization behaviour of some isomeric triaryl nitrocyclohexenes. cis-Eliminations leading to loss of HNO₂, H₂NO₂ and arene were found to be stereochemically preferred in gaseous ions.     

Quantitation of isomeric ion mixtures using collisional activation mass spectra

Recently Bass and Bowers have criticized methods for calculation of isomeric composition of gaseous ions based on mass spectra from collisionally activated dissociations (CAD). They fault values from this laboratory on the proportion of benzyl and tropylium ions calculated by two methods from product ion abundances. However, a careful remeasurement of the relevant yields of CAD product ions shows that neither calculation method affected the result outside experimental error, as the ion yields for at least 14 higher energy dissociations are insensitive to both isomeric identity and internal energy. Reducing the [C₇H₇]⁺ internal energy by 1.5 eV does give a 25% reduction in the ion yield for the lowest energy process, supporting the accepted recommendation that these be omitted for quantitative spectral comparisons. A calculation error was made in one of our previous reports on [C₇H₇]⁺, and corrected isomeric composition values are presented. The disparate values from recalculation by Bass and Bowers of other data from this laboratory on [C₂H₄O]^+˙ ions are shown here to be consistent with the large experimental error of those measurements; the medians of their values are actually near the values originally reported. In direct contrast to their assertions, we find no evidence that previous calculation methods have produced misleading conclusions, or that the assumption of linear superposition of CAD spectra in ion mixtures has yielded unreliable results.