Reactions of first-row transition-metal ions [scandium(1+) to zinc(1+)] with phenyl halides in the gas phase

Bjarnason, Ásgeir

doi:10.1021/om00051a008

Cited by 27 publications

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“…Previous gas‐phase studies on the activation of CCl bonds of chloroarenes mainly focused on the reaction between first‐row transition‐metal ions and chlorobenzene 12. 13, 15 Several transition‐metal ions, such as Sc + , Ti + , Fe + , and V + induce dehydrohalogenation, and according to the proposed mechanism,15b,c the reaction proceeds by means of an insertion into the CCl bond, followed by H transfer from the ortho ‐position to the metal and subsequent HCl elimination; however, no labeling experiments have been performed to support this suggestion. Further, the reaction of chlorobenzene with Cr + or Zn + results in chloride abstraction to form a phenyl cation; other first‐row transition metal ions like Mn + , Co + , Ni + , and Cu + have been found to be inert with respect to the activation of the CCl bond of C 6 H 5 Cl.…”

Section: Introductionmentioning

confidence: 99%

Mathematical Modeling of Ocimum basilicum L. Supercritical CO₂ Extraction

et al. 2014

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The effects of pressure and temperature on supercritical extraction of Ocimum basilicum L. in terms of extraction yield and aromatic compounds were investigated. Linalool, eugenol, and δ‐cadinene were indentified as three main compounds of the prepared extracts. The dominant compound in all investigated supercritical basil extracts was linalool. Within the experimental range the extraction parameters had a significant influence on the extraction yield. The obtained results for the sweet basil total extract, cadinene, and linalool best matched with the Gordillo et al. model, therefore, the solubility of total extract, linalool, and cadinene in supercritical CO2 at investigated temperatures is described as a function of pressure.

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Section: Introductionmentioning

confidence: 99%

Mathematical Modeling of Ocimum basilicum L. Supercritical CO₂ Extraction

et al. 2014

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“…The experimental approach has been described elsewhere, ,, but briefly, the experiments were done by employing a Millipore-Extrel FTMS-2000 Fourier transform mass spectrometer equipped with a pulsed CO 2 laser and a laser desorption interface. The experiments involving Fe + and Ti + were initially performed using a Nicolet FTMS-2000 instrument equipped with cryo- and turbomolecular pumps instead of the standard diffusion pumps.…”

Section: Methodsmentioning

confidence: 99%

“…Instrumental advances, in particular the development of Fourier transform mass spectrometers, have opened doors to more detailed analysis of ion−molecule reactions in the gas phase. In a recent paper, the reactions of Fe + with phenyl halides in the gas phase were reported and later the reactions of all the other first-row transition metal ions were studied and Freiser's group has also studied the reactions of M(benzyne) + with various substrates. , Among the interesting reactions observed in the studies mentioned above was the iron-catalyzed formation of oligomers of phenylene of the form (C 6 H 4 ) n + , with n = 2−5, from iron complex ions of the form Fe(C 6 H 4 ) n + , which in turn were produced in successive dehydrohalogenation reactions of Fe + with the phenyl halides.…”

Section: Introductionmentioning

confidence: 99%

“…The reactions of these metal ions with 1-fluoronaphthalene have been discussed in a preliminary report . The metal ions were chosen in light of the results obtained in the phenyl halide study, where Cr + , Mn + , Cu + , and Zn + were found to be either unreactive or only participate in reactions of little interest, such as the charge exchange reactions of Zn + (due to its high ionization potential).…”

Section: Introductionmentioning

confidence: 99%

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Reactions of Sc⁺, Ti⁺, V⁺, Fe⁺, Co⁺, and Ni⁺with Naphthalene Halides. Study of the Initial Steps of a Metal-Catalyzed Polymerization in the Gas Phase

Bjarnason

1996

Organometallics

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Poly(naphthylene) is of interest, in particular, due to its intrinsic electrical conductivity. Reported here are the initial steps in the metal-catalyzed polymerization of naphthalene as observed in the gas-phase reactions of Sc+, Ti+, V+, Fe+, Co+, and Ni+ with 1-halonaphthalenes studied in a Fourier transform mass spectrometer. Sc+, Ti+, V+, and Fe+ were found to dehydrohalogenate all of the halides stepwise, to produce ions of the form M(C10H6) n +. Up to 6 steps of dehydrohalogenations were observed in the case of the reactions of Fe+ with 1-chloronaphthalene. Co+ and Ni+ exhibited similar behavior except in the case of 1-fluoronaphthalene, where only condensation products were observed. Sc+ showed unusual reactivity by also being able to eliminate C2H2, this reaction being most prominent in the case of fluoronaphthalene. Aside from dehydrohalogenations, Ti+ was found to eliminate a hydrogen atom to form TiC10H6X+ in its reactions with all of the halides. 2-Bromonaphthalene was also studied and compared with the results for 1-bromonaphthalene, but no significant differences were observed. Secondary and higher order reactions were investigated, and several ionic products from primary and secondary reactions were studied by collision-induced dissociation (CID). The formation of (C10H6) n + with n = 2 and 3 was observed and was in some cases formed by loss of M or MX from M(C10H6) n + and M(C10H6) n X+, respectively, but also in direct reactions of M(C10H6) n - 1 + with the neutral halonaphthalene, which is in contrast with the behavior observed for the related phenyl halides in an earlier study. The ionization potentials of (C10H6)n with n = 2 and 3 are lower than that of iron (7.87 eV) as Fe was lost upon CID of Fe(C10H6) n + for n = 2 and 3. The thermodynamical consequences of the reactions are discussed, as well as deductions concerning the structure of several of the ionic reaction products.

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“…3 Gas-phase Zn generally reacts with neutral alkanes by charge transfer and adduct formation. [6][7][8][9][10][11] The ionization energy of the ethyl radical, C 2 H 5 Á , is 8.13 eV, 3 more than 1 eV below that of Zn. Most prior experimental studies have focused on the reactivity of bare metal cations.…”

Section: Received 25 May 1999; Accepted 25 May 1999mentioning

confidence: 99%

Self-chemical ionization of diethylzinc

Freitas

Dillon

Dougherty

et al. 1999

Rapid Commun. Mass Spectrom.

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The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.

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Reactions of first-row transition-metal ions [scandium(1+) to zinc(1+)] with phenyl halides in the gas phase

Cited by 27 publications

References 0 publications

Mathematical Modeling of Ocimum basilicum L. Supercritical CO₂ Extraction

Mathematical Modeling of Ocimum basilicum L. Supercritical CO₂ Extraction

Reactions of Sc⁺, Ti⁺, V⁺, Fe⁺, Co⁺, and Ni⁺with Naphthalene Halides. Study of the Initial Steps of a Metal-Catalyzed Polymerization in the Gas Phase

Self-chemical ionization of diethylzinc

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Reactions of first-row transition-metal ions [scandium(1+) to zinc(1+)] with phenyl halides in the gas phase

Cited by 27 publications

References 0 publications

Mathematical Modeling of Ocimum basilicum L. Supercritical CO2 Extraction

Mathematical Modeling of Ocimum basilicum L. Supercritical CO2 Extraction

Reactions of Sc+, Ti+, V+, Fe+, Co+, and Ni+with Naphthalene Halides. Study of the Initial Steps of a Metal-Catalyzed Polymerization in the Gas Phase

Self-chemical ionization of diethylzinc

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Mathematical Modeling of Ocimum basilicum L. Supercritical CO₂ Extraction

Mathematical Modeling of Ocimum basilicum L. Supercritical CO₂ Extraction

Reactions of Sc⁺, Ti⁺, V⁺, Fe⁺, Co⁺, and Ni⁺with Naphthalene Halides. Study of the Initial Steps of a Metal-Catalyzed Polymerization in the Gas Phase