Isomerization and fragmentation reactions of gaseous phenylarsane radical cations and phenylarsanyl cations. A study by tandem mass spectrometry and theoretical calculations

The unimolecular reactions of radical cations and cations derived from phenylarsane, C6H5AsH2 (1) and dideutero phenylarsane, C6H5AsD2 (1-d2), were investigated by methods of tandem mass spectrometry and theoretical calculations. The mass spectrometric experiments reveal that the molecular ion of phenylarsane, 1*+, exhibits different reactivity at low and high internal excess energy. Only at low internal energy the observed fragmentations are as expected, that is the molecular ion 1*+ decomposes almost exclusively by loss of an H atom. The deuterated derivative 1-d2 with an AsD2 group eliminates selectively a D atom under these conditions. The resulting phenylarsenium ion [C6H5AsH]+, 2+, decomposes rather easily by loss of the As atom to give the benzene radical cation [C6H6]*+ and is therefore of low abundance in the 70 eV EI mass spectrum. At high internal excess energy, the ion 1*+ decomposes very differently either by elimination of an H2 molecule, or by release of the As atom, or by loss of an AsH fragment. Final products of these reactions are either the benzoarsenium ion 4*+, or the benzonium ion [C6H7]+, or the benzene radical cation, [C6H6]*+. As key-steps, these fragmentations contain reductive eliminations from the central As atom under H-H or C-H bond formation. Labeling experiments show that H/D exchange reactions precede these fragmentations and, specifically, that complete positional exchange of the H atoms in 1*+ occurs. Computations at the UMP2/6-311+G(d)//UHF/6-311+G(d) level agree best with the experimental results and suggest: (i) 1*+ rearranges (activation enthalpy of 93 kJ mol(-1)) to a distinctly more stable (DeltaH(r)(298) = -64 kJ mol(-1)) isomer 1 sigma*+ with a structure best represented as a distonic radical cation sigma complex between AsH and benzene. (ii) The six H atoms of the benzene moiety of 1 sigma*+ become equivalent by a fast ring walk of the AsH group. (iii) A reversible isomerization 1+<==>1 sigma*+ scrambles eventually all H atoms over all positions in 1*+. The distonic radical cation 1*+ is predisposed for the elimination of an As atom or an AsH fragment. The calculations are in accordance with the experimentally preferred reactions when the As atom and the AsH fragment are generated in the quartet and triplet state, respectively. Alternatively, 1*(+) undergoes a reductive elimination of H2 from the AsH2 group via a remarkably stable complex of the phenylarsandiyl radical cation, [C6H5As]*+ and an H2 molecule.     

Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2*+ (E = N, P, As)

In context of an analysis of the effect of the central atom E of gaseous radical cations of phenyl pnictogens C(6)H(5)EH(2), E = N (1), P (2), and As (3), the mass spectrometric reactions of phenyl phosphane 2 have been re-investigated by D-labeling and by using methods of tandem mass spectrometry. The 70 eV mass spectrum of 2 shows the base peak for ion [M-2H](*+) and significant peaks for ions [M-H](+), [M-(2C,3H)](+), [M-PH] (*+), and [M-(C,P,2H)](+). Metastable 2(*+) fragments exclusively by loss of H(2), and the investigation of deuterated 2-d(2) shows that excessive H/D migrations occur before fragmentation. Other significant fragment ions in the mass spectrum of 2 arise by losses of C(2)H(2,) P, or HCP from the ion [M-H](+). This mass spectrometric behavior puts the radical cation 2(*+) in between the fragmentation reactions of aniline radical cation 1(*+) (loss of H and subsequent losses of C(2)H(2,) or HCN) and phenyl arsane radical cation 3(*+) (elimination of H(2) and loss of As from ion [M-H](+)). The fragmentation mechanisms of the radical cations 1(*+) -3(*+) and of related ions were analyzed by calculations of the enthalpy of relevant species at the stationary points of the minimum enthalpy reaction pathways using the DFT hybrid functionals UBHLYP/6-311+G(2d,p)//UBHLYP/6-311+G(d). The results show that, in contrast to ionized aniline 1(*+), the reactions of the derivatives 2(*+) and 3(*+) of the heavier main group elements P and As are characterized by an easy elimination of H(2)via a reductive elimination of group C(6)H(5)-E (E = P, As) and by a special stability of bicyclic isomers of 2(*+) and 3(*+). Thus, while 1(*+) rearranges by ring expansion and formation an 7-aza-tropylium cation by loss of H., the increased stability of bicyclic intermediates in the rearrangement of 2(*+) and in particular of 3(*+) results in separate rearrangement pathways. The origin of these effects is the more extended and diffuse nature of the 3p and 4p AO of P and As.     

EPR studies of amine radical cations. Part 2. Thermal and photo-induced rearrangements of propargylamine and allylamine radical cations in low-temperature freon matrices

Matrix EPR studies and quantum chemical calculations have been used to characterize the consecutive H-atom shifts undergone by the nitrogen-centered parent radical cations of propargylamine (1b*+) and allylamine (5*+) on thermal or photoinduced activation. The radical cation rearrangements of these unsaturated parent amines occur initially by a 1,2 H-atom shift from C1 to C2 with pi-bond formation at the positively charged nitrogen; this is followed by a consecutive reaction involving a second H-atom shift from C2 to C3. Thus, exposure to red light (lambda > 650 nm) converts 1b*+ to the vinyl-type distonic radical cation 2*+ which in turn is transformed on further photolysis with blue-green light (lambda approximately 400-600 nm) to the allene-type heteroallylic radical cation 3*+. Calculations show that the energy ordering is 1b*+ > 2*+ > 3*+, so that the consecutive H-atom shifts are driven by the formation of more stable isomers. Similarly, the parent radical cation of allylamine 5*+ undergoes a spontaneous 1,2-hydrogen atom shift from C1 to C2 at 77 K with a t1/2 of approximately 1 h to yield the distonic alkyl-type iminopropyl radical cation 6*+; this thermal reaction is attributed largely to quantum tunneling, and the rate is enhanced on concomitant photobleaching with visible light. Subsequent exposure to UV light (lambda approximately 350-400 nm) converts 6*+ by a 2,3 H-shift to the 1-aminopropene radical cation 7*+, which is confirmed to be the lowest-energy isomer derived from the ionization of either allylamine or cyclopropylamine. Although the parent radical cations of N, N-dimethylallylamine (9*+) and N-methylallylamine (11*+) are both stabilized by the electron-donating character of the methyl group(s), the photobleaching of 9*+ leads to the remarkable formation of the cyclic 1-methylpyrrolidine radical cation 10*+. The first step of this transformation now involves the migration of a hydrogen atom to C2 of the allyl group from one of the methyl groups (rather than from C1); the reaction is then completed by the cyclization of the generated MeN + (=CH2) CH2CH2CH2* distonic radical cation, possibly in a concerted overall process. In contrast to the ubiquitous H-atom transfer from carbon to nitrogen that occurs in the parent radical cations of saturated amines, the alternate rearrangements of either 1b*+ or 5*+ to an ammonium-type radical cation by a hypothetical H-atom shift from C1 to the ionized NH2 group are not observed. This is in line with calculations showing that the thermal barrier for this transformation is much higher (approximately 120 kJ mol-1) than those for the conversion of 1b*+ --> 2*+ and 5*+--> 6*+ (approximately 40-60 kJ mol-1).     

A ring walk of methylene groups in toluene radical cations. An extension of the toluene-cycloheptatriene rearrangement of aromatic radical cations. Theory and experiment

The minimum energy reaction pathway (MERP) of the toluene-cycloheptatriene radical cation rearrangement (TOL/CHT-rearrangement) has been calculated by the UHF and DFT model at the level UHF/6-311+G(3df,2p)//UHF/6-31G(d) and B3LYP/6-311+G(3df,2p)//B3LYp/6-31G(d), respectively, including the ring walk of the substituent by a 1,2-shift around the aromatic ring. This ring walk corresponds to interconversion of distonic ions and norcaradiene radical cations (the two intermediates of the TOL/CHT-rearrangement) by making and breaking of the external C-C bonds of the cyclopropane moiety of the intermediate norcaradiene structure. For toluene radical cation 1, UHF calculations adequately reproduce earlier results(4) and show, that the ring walk of the CH(3)-substituents requires slightly more energy than formation of the cycloheptatriene radical cation. By the DFT model, the distonic ion, which is formed initially by a 1,2-H shift from CH(3) to the benzene ring, is not stable but the transition state of an interconversion of norcaradiene radical cations along a ring walk of the CH(3) substituent. The activation energy for this ring walk exceeds that for formation of the cycloheptatriene radical cation by c. 30 kJ mol(-1). Thus, isomerization of 1 by a ring walk of the CH(3)-substituent competes with the TOL/CHT-rearrangement likely only for excited 1. The calculation was repeated for the MERPs of a TOL/CHT-rearrangement of para-xylene radical cation 5 and ethylbenzene radical cation 2, yielding basically the same results as for 1. According to the calculation, polar substituents alter significantly the relative energies of the competing routes of isomerization. For benzylcyanide 3 (X = CN), the activation energy for a ring walk of the NC-CH(2)-substituent is distinctly below that of a ring enlargement. For benzyl methyl ether 4 (X = OCH(3)), the distonic intermediate along the UHF-MERP is unusually stable. Further, the 7-methoxy-norcaradiene radical ion is unstable and corresponds to a transition state between isomeric distonic intermediates differing by a 1,2-shift of the side chain. In contrast, the 7-methoxy-norcaradiene radical ion is the only intermediate of the DFT-MERP, and the distonic ion is the transition state for a 1,2-shift of the cyclopropane ring. A ring walk of the CH(3)OCH(2)-substituent is much more favorable than formation of a 7-methoxy-cycloheptatriene radical cation in both MERPs. The findings of the theoretical calculation are substantiated by the mass spectrometric fragmentations of meta- and para-methoxymethylated 1-phenylethanols 8 and 9 and of para-methoxymethyl substituted benzyl ethyl ether 10 and benzyl n-propyl ether 11. Important fragmentation routes of metastable molecular ions of these compounds correspond to elimination of alcohols. Use of deuterated derivatives shows that the elimination occurs by a "false" ortho-effect which requires migration of a ROCH(2)-substituent around the benzene ring. Results of particular interest are obtained for the asymmetric bis-ethers 10 and 11. Here, the MIKE spectra of the molecular ions of deuterated analogs reveal a selective ring walk of the C(2)H(5)OCH(2)- and n-C(3)H(7)OCH(2)-side chain, respectively.     

The rearrangement of the cubane radical cation in solution

The rearrangement of the cubane radical cation (1*+) was examined both experimentally (anodic as well as (photo)chemical oxidation of cubane 1 in acetonitrile) and computationally at coupled cluster, DFT, and MP2 [BCCD(T)/cc-pVDZ//B3LYP/6-31G* ZPVE as well as BCCD(T)/cc-pVDZ//MP2/6-31G* + ZPVE] levels of theory. The interconversion of the twelve C2v degenerate structures of 1*+ is associated with a sizable activation energy of 1.6 kcalmol(-1). The barriers for the isomerization of 1*- to the cuneane radical cation (2*+) and for the C-C bond fragmentation to the secocubane-4,7-diyl radical cation (10*+) are virtually identical (deltaH0++ = 7.8 and 7.9 kcalmol(-1), respectively). The low-barrier rearrangement of 10*+ to the more stable syn-tricyclooctadiene radical cation 3*+ favors the fragmentation pathway that terminates with the cyclooctatetraene radical cation 6*+. Experimental single-electron transfer (SET) oxidation of cubane in acetonitrile with photoexcited 1,2,4,5-tetracyanobenzene, in combination with back electron transfer to the transient radical cation, also shows that 1*+ preferentially follows a multistep rearrangement to 6*+ through 10*+ and 3*+ rather than through 2*+. This was confirmed by the oxidation of syn-tricyclooctadiene (3), which, like 1, also forms 6 in the SET oxidation/rearrangement/electron-recapture process. In contrast, cuneane (2) is oxidized exclusively to semibullvalene (9) under analogous conditions. The rearrangement of 1*+ to 6*+ via 3*+, which was recently observed spectroscopically upon ionization in a hydrocarbon glass matrix, is also favored in solution.     

Reactivity of triarylphosphine peroxyl radical cations generated through the reaction of triarylphosphine radical cations with oxygen

One-electron oxidation of triarylphosphines (Ar3P, Ar = phenyl and substituted phenyl) in benzonitrile (PhCN) has been studied using pulse radiolysis technique. One-electron oxidation of Ar3P occurred to yield the radical cation (Ar3P*+) which showed an intense absorption with a peak at 360-370 nm together with a broad band at 500-600 nm. The addition of molecular oxygen (O2) to the phosphorus atom of Ar3P*+ took place at the second-order rate constant of 10(7)-10(9) dm(3) mol(-1) s(-1) to yield the peroxyl triarylphosphinyl radical cation (Ar3P+OO*). It is found that the electron-releasing substituents on the para position of the phenyl ring of Ar3P influence the rate constants of the reaction of Ar3P*+ with O2 and that o-methyl substituents on the phenyl ring influence the reactivity of Ar3P+OO*.     

Gas-phase electrophilic addition promoted by CH(3)S(+)=CH(2) ions on aromatic systems

The gas-phase methylenation reaction between CH(3)S(+)=CH(2) and alkylbenzenes, aniline, phenol and alkyl phenyl ethers, which yields [M + CH](+) and CH(3)SH, has been studied by Fourier transform ion cyclotron resonance (FT-ICR) techniques and computational chemistry at the DFT level. The methylthiomethyl cation is less reactive than methoxymethyl and, unlike the latter, is unreactive toward benzene. The calculations suggest that reaction with toluene should proceed primarily by addition at the para and ortho positions resulting in a benzyl-type ion. Reaction with aniline-2,3,4,5,6-d(5) reveals that elimination of CH(3)SD is kinetically favored by a factor of 5 over elimination of CH(3)SH. Experiments with C(6)H(6)ND(2) and theoretical calculations suggest that methylenation at the nitrogen atom is energetically favorable and likely, but the observed results may reflect some H/D scrambling, which occurs after attack at a ring position. By comparison, reaction with phenol-2,3,4,5,6-d(5) reveals that methylenation followed by elimination of CH(3)SD is kinetically favored by a factor of 3.8 over elimination of CH(3)SH. For phenol, the theoretical calculations suggest that attack by CH(3)S(+)=CH(2) at the para or ortho position is the only low-energy pathway for methylenation. However, a low-energy pathway for hydrogen scrambling is predicted by the calculations originating from the exit complex, [CH(3)SH(...) CH(2)=C(6)H(4)=OH](+), of reaction at a ring position.     

A computational study on the substituent effects and product stereoselectivity of the intermolecular formal aza-[3+3] cycloaddition reaction between vinylogous amides and α,β-unsaturated imine cations

The substituent effects and product stereoselectivity of the title reaction has been studied using density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level of theory. It was found that the substituents do not perturb the mechanism of intermolecular formal aza-[3+3] cycloaddition. Our calculations also show that methyl or benzyl groups on the N atom of vinylogous amide favor the addition step, but alkyl substituents on the either N atom or terminal C atom of α,β-unsaturated imine cation have opposite effects. Alkyl substituents on the N atom of α,β-unsaturated imine cation may lower the activation barriers for elimination of amide. The steric interaction between two substituents leads to the formation of major product both thermodynamically and kinetically.     

Incorporation of 2-arylhexa-1,5-diene into pentasil zeolite: A distorted 1-arylcyclohexane-1,4-diyl radical cation at room temperature

Incorporation into a redox-active pentasil zeolite [(Na,H)-ZSM-5] converted 2-arylhexa-1,5-dienes (9a-c; aryl = phenyl, tolyl, anisyl) into 1-arylcyclohexane-1,4-diyl radical cations, 10a-c*+. The ESR spectra of 10a-c*+ (six lines, g = 2.0026; a = 9.0 G) indicated the presence of five essentially equivalent nuclei, indicating limited delocalization of spin and charge into the phenyl group. Sequestered in the pores of ZSM-5, the three species 10a-c*+ are stable at room temperature, in striking contrast to the parent radical cation in cryogenic matrices: cyclohexane-1,4-diyl radical cation is converted to cyclohexene radical cation above 90 K. The structures of radical cation 10a*+ (X = H) and of the unsubstituted parent were probed by density functional theory (DFT) and ab initio calculations.     

Product detection of the CH radical reaction with acetaldehyde

The reaction of the methylidyne radical (CH) with acetaldehyde (CH(3)CHO) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of CHBr(3) and react with acetaldehyde in an excess of helium and nitrogen gas flow. Five reaction exit channels are observed corresponding to elimination of methylene (CH(2)), elimination of a formyl radical (HCO), elimination of carbon monoxide (CO), elimination of a methyl radical (CH(3)), and elimination of a hydrogen atom. Analysis of the photoionization yields versus photon energy for the reaction of CH and CD radicals with acetaldehyde and CH radical with partially deuterated acetaldehyde (CD(3)CHO) provides fine details about the reaction mechanism. The CH(2) elimination channel is found to preferentially form the acetyl radical by removal of the aldehydic hydrogen. The insertion of the CH radical into a C-H bond of the methyl group of acetaldehyde is likely to lead to a C(3)H(5)O reaction intermediate that can isomerize by β-hydrogen transfer of the aldehydic hydrogen atom and dissociate to form acrolein + H or ketene + CH(3), which are observed directly. Cycloaddition of the radical onto the carbonyl group is likely to lead to the formation of the observed products, methylketene, methyleneoxirane, and acrolein.     

Factors controlling the alkyne prins cyclization: the stability of dihydropyranyl cations

The relative stability of the intermediates involved in the alkyne Prins cyclization and the competitive 2-oxonia-[3,3]-sigmatropic rearrangement was studied. This rearrangement was shown to occur slowly under typical alkyne Prins cyclization conditions when the allenyl oxocarbenium ion that results from the rearrangement is similar to or higher in energy than the starting alkynyl oxocarbenium ion. The formal 2-oxonia-[3,3]-sigmatropic rearrangement may be disfavored by destabilizing the resultant allenyl oxocarbenium ion or by stabilizing an intermediate dihydropyranyl cation. The trimethylsilyl group as a substituent at the alkyne and electron-withdrawing groups (CH2Cl and CH2CN) located at the alpha-position to the carbinol center are shown to be effective. DFT calculations suggest that these substituents stabilize the dihydropyranyl cations, thus leading to a more uniform reorganization of the electronic density in the ring, and do not have a direct effect on the formally positively charged carbon atom.     

Role of 2-oxo and 2-thioxo modifications on the fragmentation reactions of the histidine radical cation

The fragmentation reactions of the radical cations, M(·+), of histidine, 2-oxo-histidine and 2-thioxo-histidine were examined using a combination of experiments performed on a linear ion trap and density functional theory (DFT) calculations at the UB3-LYP/6-311++G(d,p) level of theory. Low-energy collision-induced dissociation (CID) on [Cu(II)(terpy)(M)](2+) complexes, formed via electrospray ionisation, produced the radical cations in sufficient yield to examine their unimolecular chemistry via an additional stage of CID. The CID spectrum of the radical cation of histidine is dominated by loss of water with the next most abundant ion arising from the combined loss of H(2)O and CO. In contrast, the CID spectra of the radical cations of 2-oxo-histidine and 2-thioxo-histidine are dominated by the combined loss of CO(2) and NH=CH(2). The observed differences are rationalised via DFT calculations which reveal that the barrier associated with loss of CO(2) from the histidine radical cation is higher than that for loss of H(2)O. In contrast, the introduction of an oxygen or sulfur atom into the side chain of histidine results in a reversal of the order of these barrier heights, thus making CO(2) loss the preferred pathway.     

Substituent effects on the energies of the electronic transitions of geminally diphenyl-substituted trimethylenemethane (TMM) radical cations. Experimental and theoretical evidence for a twisted molecular and localized electronic structure

Substituent effects on the energies (Eob) of electronic transitions of geminally diphenyl-substituted trimethylenemethane (TMM) radical cations 5a-k*+ and those of structurally related 1,1-diarylethyl cations 7a-k+ were determined experimentally by using electronic transition spectroscopy. In addition, transition energies of these radical cations were determined by using density functional theory (DFT) and time-dependent (TD)-DFT calculations. The electronic transition bands of 5a-k*+ and 7a-k+ have maxima (lambdaob) that appear at 500-432 and 472-422 nm, respectively. A Hammett treatment made by plotting the Eob values relative to that of the diphenyl-TMM radical cation 5d*+ (DeltaEob) vs the cationic substituent parameter sigma+ give a favorable correlation with a boundary point at sigma+ = 0.00 and a positive rho for sigma+ < 0 and a negative rho for sigma+ > 0. A comparison of the lambdaob and rho values for 5a-k*+ and 7a-k+ suggests that the chromophore of 5*+ is substantially the same as that of 7+. The results of TD-DFT calculations, which reproduce the experimental electronic transition spectra and relationships between DeltaEob and sigma+, and suggest that the absorption band of 5*+ is associated with the SOMO-X --> SOMO transition, while that of 7+ is due to the HOMO --> LUMO transition. Another interesting observation is that Cl and Br substituents in the diphenyl-substituted TMM radical cations and 1,1-diarylethyl cations 7a-k+ act as electron-donating groups in terms of their effect on the corresponding electronic transitions. The results show that the molecular structure of 5*+ is a considerably twisted and that 5*+ has a substantially localized electronic state in which the positive charge and odd electron are localized in the respective diarylmethyl and the allyl moieties.     

Characterization by theory of H-transfers and onium reactions of CH<Subscript>3</Subscript>CH<Subscript>2</Subscript>CH<Subscript>2</Subscript>N<Superscript>+</Superscript>H=CH<Subscript>2</Subscript>

H-transfers by 4-, 5-, and 6-membered ring transition states to the pi-bonded methylene of CH3CH2CH2NH+=CH2 (1) are characterized by theory and compared with the corresponding transfers in cation radicals. Four-membered ring H-transfers converting 1 to CH3CH2CH=N+HCH3 (2) and CH3N+H=CH2 to CH2=NH+CH3 are high-energy processes involving rotation of the source and destination RHC= groups (R = H or C2H5) to near bisection by skeletal planes; migrating hydrogens move near these planes. The H-transfer 1 --> CH3C+HCH2NHCH3 (3) has a higher energy transition-state than 1 --> 2, in marked contrast to the corresponding relative energies of 4- and 5-membered ring H-transfers in cation-radicals. Six-membered ring H-transfer-dissociation (1 --> CH2=CH2 + CH2=N+HCH3) is a closed shell analog of the McLafferty rearrangement. It has a lower energy transition-state than either 1 --> 2 or 1 --> 3, but is still a much higher energy process than 6-membered ring H-transfers in aliphatic cation radicals. In contrast to the stepwise McLafferty rearrangement in cation radicals, H-transfer and CC bond breaking are highly synchronous in 1 --> CH3N+H=CH2 + CH2=CH2. H-transfers in propene elimination from 1 are ion-neutral complex-mediated: 1--> [CH3CH2CH2+ ---NH=CH2] --> [CH3C+HCH3 NH=CH2] --> CH3CH = CH2 + CH2=NH2+. Intrinsic reaction coordinate tracing demonstrated that a slight preference for H-transfer from the methyl containing the carbon from which CH2=NH is cleaved is due to CH2=NH passing nearer this methyl than the other on its way to abstracting H, i.e., some memory of the initial orientation of the partners accompanies this reaction.     

Hydrogen bonding interactions of pyridine*+ with water: stepwise solvation of distonic cations

The solvation energies of the pyridine*+ radical cation by 1-4 H2O molecules were determined by equilibrium measurements in a drift cell. The binding energies of the pyridine*+(H2O)n clusters are similar to the binding energies of protonated pyridine-water clusters, (C5H5NH+)(H2O)n, which involve NH+..OH2 bonds and different from those of the solvated benzene radical cation-water clusters, C6H6*+(H2O)n, which involve CHdelta+..OH2 bonds. These relations indicate that the observed pyridine*+ ions have the distonic *C5H4NH+ structures that can form NH+..OH2 bonds. The observed thermochemistry and ab initio calculations show that these bonds are not affected significantly by an unpaired electron at another site of the ion. Similar observations also identify the 2-fluoropyridine*+ distonic ion. The distonic structure is also consistent with the reactivity of pyridine*+ in H atom transfer, intra-cluster proton transfer and deprotonation reactions. The results present the first measured stepwise solvation energies of distonic ions, and demonstrate that cluster thermochemistry can identify distonic structures.     

EPR studies of amine radical cations, part 1: thermal and photoinduced rearrangements of n-alkylamine radical cations to their distonic forms in low-temperature freon matrices

The thermal and photochemical transformations of primary amine radical cations (n-propyl 1.+, n-butyl 5.+) generated radiolytically in freon matrices have been investigated by using low-temperature EPR spectroscopy. Assignment of the spectra was facilitated by parallel studies on the corresponding N,N-dideuterioamines. The identifications were supported by quantum chemical calculations on the geometry, electronic structure, hyperfine splitting constants and energy levels of the observed transient radical species. The rapid generation of the primary species by a short exposure (1-2 min) to electron-beam irradiation at 77 K allowed the thermal rearrangement of 1.+ to be monitored kinetically as a first-order reaction at 125-140 K by the growth in the well-resolved EPR signal of the distonic radical cation .C(2CH2CH2NH3+. By comparison, the formation of the corresponding .CH2CH2CH2CH2NH3+ species from 5.+ is considerably more facile and already occurs within the short irradiation time. These results directly verify the intramolecular hydrogen-atom migration from carbon to nitrogen in these ionised amines, a reaction previously proposed to account for the fragmentation patterns observed in the mass spectrometry of these amines. The greater ease of the thermal rearrangement of 5.+ is in accordance with calculations on the barrier heights for these intramolecular 1,5- and 1,4-hydrogen shifts, the lower barrier for the former being associated with minimisation of the ring strain in a six-membered transition state. For 1.+, the 1,4-hydrogen shift is also brought about directly at 77 K by exposure to approximately 350 nm light, although there is also evidence for the 1,3-hydrogen shift requiring a higher energy. A more surprising result is the photochemical formation of the H2C=N. radical as a minor product under hard-matrix conditions in which diffusion is minimal. It is suggested that this occurs as a consequence of the beta-fragmentation of 1.+ to the ethyl radical and the CH2=NH2+ ion, followed by consecutive cage reactions of deprotonation and hydrogen transfer from the iminonium group. Additionally, secondary ion-molecule reactions were studied in CFCl2CF2Cl under matrix conditions that allow diffusion. The propane-1-iminyl radical CH3CH2CH=N. was detected at high concentrations of the n-propylamine substrate. Its formation is attributed to a modified reaction sequence in which 1.+ first undergoes a proton transfer within a cluster of amine molecules to yield the aminyl radical CH3CH2CH2N.H. A subsequent disproportionation of these radicals can then yield the propane-1-imine precursor CH3CH2CH=NH, which is known to easily undergo hydrogen abstraction from the nitrogen atom. The corresponding butane-1-iminyl radical was also observed.     

Gas-phase reactions of aryl radicals with 2-butyne: experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH(3)C≡CCH(3)) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH(3) loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP+2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C(4) side-chain, followed by cyclization and/or low-energy H atom β-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph˙)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH(3) loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid molecular weight growth reactions to yield polycyclic aromatic nitrogen hydrocarbons (PANHs).     

Substituted 3-phenylpropenoates and related analogs: electron ionization mass spectral fragmentation and density functional theory calculations

Analysis of ethyl 3-(2-chlorophenyl)propenoate by electron ionization mass spectrometry showed the distinct loss of an ortho chlorine. To characterize the structural requisites for the observed mass fragmentation, a series of 30 halogen-substituted 3-phenylpropenoate-related structures were examined. All ester-containing alkene derivatives exhibited loss of the distinctive chlorine from the 2-position of the phenyl ring. Analogous derivatives with the halogen (chlorine or bromine) in the para position did not evidence selective halogen loss. Results demonstrated that substituted 3-phenylpropenoates and their analogs fragment via the formation of a previously reported benzopyrylium intermediate. To understand the correlation between the intramolecular radical substitution and the abundance and selectivity of the chlorine (or other halogen) displacement, density functional theory calculations were performed to determine the charge on the principal cation involved in the chlorine loss (in the ortho, meta, and para positions), the charge for the neutral radical (noncation), the excess alpha-electron density on the relevant atom and the energy to form the cation from the neutral atom (ionization energy). Results showed that the selectivity and extent of halogen displacement correlated highly to the electrophilicity of the radical cation as well as the neutral radical. These data further support the proposed fragmentation mechanism involving intramolecular radical elimination.     

Tunneling in the loss of hydrogen chloride from isopropyl chloride cation

The unimolecular dissociation of isopropyl chloride cation has been investigated using mass-analyzed ion kinetic energy spectrometry. The C3H6*+ ion was the only product ion in the metastable dissociation. The kinetic energy release distribution for the HCl loss was determined. Ab initio molecular orbital calculations were performed at the MP2/6-311++G(d,p) level together with single point energy calculations at the QCSID(T)/6-311++G(2d,2p) level. The calculations show that the molecular ion rearranges to an ion-dipole complex prior to loss of HCl via a transition state containing a four-membered ring. The rearrangement involves H atom transfer. On the basis of the potential energy surface obtained for the loss of HCl and Cl*, the rate constants were calculated by transition-state statistical theories with considering tunneling effect. From the calculated result, it is proposed that the observed HCl loss would occur via tunneling through the barrier for isomerization to the ion-dipole complex, CH3CHCH2*+...HCl.     

Competitive decay pathways of the radical ions formed by photoinduced electron transfer between quinones and 4,4'-dimethoxydiphenylmethane in acetonitrile

The reactivity of the cation radical of (4-MeOC6H4)2CH2 photosensitized by 1,4-benzoquinone (BQ), 2,5-dichloro-1,4-benzoquinone (Cl2BQ), and tetrachloro-1,4-benzoquinone (chloranil, CA) was investigated in acetonitrile. The main photoreaction products obtained by steady-state irradiation were identified to be: (4-MeOC6H4)2-CHOC6H4OH, sensitized by BQ; (4-MeOC6H4)2CHCl, sensitized by Cl2BQ; (4-MeOC6H4)2CHOH, sensitized by CA. The mechanism of their formation was investigated by nanosecond laser flash photolysis that allowed transient species (radical ions, neutral radicals, and ions) to be detected and characterized in terms of absorption spectra, formation quantum yields, and decay rate constants. For all systems, the interaction between the triplet quinone (Q) and (4-MeOC6H4)2CH2 produced the corresponding radical ions (quantum yield phi > or = 0.72) which mainly decay by back electron transfer processes. Less efficient reaction routes for the radical ions Q*- and (4-MeOC6H4)2CH2*+ were also: i) the proton-transfer process with the formation of the radical (4-MeOC6H4)2CH* by use of Cl2BQ; ii) the hydrogen-transfer process with the formation of the cation (4-MeOC6H4)2CH+ in the case of CA. Instead. BQ sensitized a much higher yield of BOH* and (4-MeOC6H4)2CH*, mainly by the direct interaction of triplet BQ with (4-MeOC6H4)2CH2. It was also shown that the presence of salts decreases significantly the rate of the back electron transfer process and enhances the quantum yields of formation of the neutral radicals and ions when Cl2BQ and CA are used, respectively. The behavior of BQ*-, Cl2BQ*-, and CA*- appears to be mainly determined by the Mulliken charges on the oxygen atom obtained from quantum mechanical calculations with the model B3LYP/6-311G(d,p). Spin densities seem to be much less important.