Reactions of CoCp+ (Cp = cyclopentadienyl) with hydrocarbons in the gas phase. Observation of novel skeletal isomerizations/dehydrocyclizations resulting in cobaltocenium formation

Jacobson, D. B.; Freiser, Ben S.

doi:10.1021/ja00311a030

Cited by 48 publications

(40 citation statements)

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“…In a previous study, Jacobson and Freiser reported that double H 2 loss is twice as abundant in the CpCo ⅐ϩ ion reactions with n-pentane and n-hexane as single H 2 loss [21]. Our results suggest that double H 2 loss dominates when a sufficient number of C™C sites are available.…”

Section: Single and Double Dehydrogenationsupporting

confidence: 60%

“…Dehydrogenation by the CpCo ⅐ϩ ion has been classified an oxidative addition/reductive elimination reaction for small alkane systems [16,21]. A similar type reaction likely occurs for the alkanes studied here.…”

Section: Single and Double Dehydrogenationmentioning

confidence: 65%

“…Collision-activated dissociation measurements on smaller alkane systems support the above rationale. In an earlier study, Jacobson and Freiser observed that collision activated dissociation measurements of the DD product for the CpCo-pentane and CpCo-hexane ion systems yielded a cobaltocenium-type product [21].…”

Section: Single and Double Dehydrogenationmentioning

confidence: 99%

“…A similar type reaction likely occurs for the alkanes studied here. It is thought that the CpCo ⅐ϩ ion preferentially attacks the C™H bond in the initial oxidative addition step due to the strong s character of metal-ligand antibonding orbital, i.e., LUMO (lowest unoccupied molecular orbital) [21]. It is interesting that the CpCo ⅐ϩ ion reacts with n-alkanes exclusively by dehydrogenation, while the Co ϩ ion reacts by dehydrogenation and dealkylation [15][16][17]31].…”

Section: Single and Double Dehydrogenationmentioning

confidence: 99%

“…Not only is it the most reactive of the CpM ϩ ions, but with small alkanes (n ϭ 2-6) it reacts exclusively with C™H bonds and not C™C bonds [20,21]. Reaction products consist of CpCo ⅐ϩ bound to a hydrocarbon formed by eliminating hydrogen molecules from the reactant alkane.…”

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confidence: 99%

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Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30

Byrd

Guttman

Ridge

2003

J. Am. Soc. Mass Spectrom.

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The present study demonstrates the feasibility of the 5 -cyclopentadienylcobalt ion (CpCo ⅐ϩ ) as a suitable cationization reagent for saturated hydrocarbon analysis by mass spectrometry. Ion/molecule reactions of CpCo ⅐ϩ and three medium chain-length n-alkanes were examined using Fourier-transform ion cyclotron resonance mass spectrometry. Second-order rate constants and reaction efficiencies were determined for the reactions studied. Loss of two hydrogen molecules from the CpCo-alkane ion complex was found to dominate all reactions (Ն80%). Furthermore, this dehydrogenation reaction efficiency increases with increasing chain length. These preliminary results suggest that the CpCo ⅐ϩ ion may be a promising cationization reagent of longer chain saturated hydrocarbons and polyolefins.

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Section: Single and Double Dehydrogenationsupporting

confidence: 60%

Section: Single and Double Dehydrogenationmentioning

confidence: 65%

Section: Single and Double Dehydrogenationmentioning

confidence: 99%

Section: Single and Double Dehydrogenationmentioning

confidence: 99%

mentioning

confidence: 99%

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Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30

Byrd

Guttman

Ridge

2003

J. Am. Soc. Mass Spectrom.

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Mass Spectrometry of Organocobalt Derivatives

Koszinowski

2022

Patai's Chemistry of Functional Groups

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Being one of the most powerful and versatile analytical techniques, mass spectrometry has greatly contributed to the analysis of organocobalt derivatives. After a short discussion of the ionization methods most relevant to the investigation of these species, this chapter reviews the application of mass spectrometry to the analysis of the title compounds. First, these applications include the characterization of preformed organocobalt derivatives, such as cobalt complexes with σ‐bound organyl groups, cobalt complexes with organic π‐donor ligands, and carbonyl‐containing cobalt clusters. In these cases, mass spectrometry is typically used as a routine technique, together with additional analytical methods. Second, mass spectrometry, particularly its electrospray‐ionization (ESI) variant, can also be employed for the detection and identification of in situ formed organocobalt derivatives. While ESI mass spectrometry is limited to the analysis of charged species, this method has succeeded in the observation of several quasi‐neutral organocobalt intermediates bearing a charged tag. From the time profiles of the ESI signal intensities of these intermediates, valuable information on the reaction kinectics could also be obtained. Finally, mass spectrometry has been extensively applied to the gas‐phase preparation and analysis of organocobalt derivatives. In the highly diluted gas phase, even very reactive organocobalt ions can be generated and further examined. Tandem‐spectrometry permits the mass selection of these ions and thereby greatly facilitates their analysis. Thus, gas‐phase experiments probing the uni‐ and bimolecular reactivity of organocobalt ions have afforded seminal thermochemical and mechanistic information. Coupling tandem mass spectrometry with gas‐phase spectroscopy has moreover furnished insight into the structures of organocobalt ions.

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Auf dem Weg zu Oligocyclopentadienyl‐Liganden: Synthese und erste Reaktionen der beiden isomeren Tercyclopentadienyle und ihrer Übergangsmetallkomplexe

Boese¹,

Myrabo

Newman

et al. 1990

Angewandte Chemie

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Reactions of CoCp+ (Cp = cyclopentadienyl) with hydrocarbons in the gas phase. Observation of novel skeletal isomerizations/dehydrocyclizations resulting in cobaltocenium formation

Cited by 48 publications

References 0 publications

Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30

Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30

Mass Spectrometry of Organocobalt Derivatives

Auf dem Weg zu Oligocyclopentadienyl‐Liganden: Synthese und erste Reaktionen der beiden isomeren Tercyclopentadienyle und ihrer Übergangsmetallkomplexe

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Reactions of CoCp+ (Cp = cyclopentadienyl) with hydrocarbons in the gas phase. Observation of novel skeletal isomerizations/dehydrocyclizations resulting in cobaltocenium formation

Cited by 48 publications

References 0 publications

Molecular mass determination of saturated hydrocarbons: reactivity of η5-cyclopentadienylcobalt ion (CpCo·+) and linear alkanes up to C-30

Molecular mass determination of saturated hydrocarbons: reactivity of η5-cyclopentadienylcobalt ion (CpCo·+) and linear alkanes up to C-30

Mass Spectrometry of Organocobalt Derivatives

Auf dem Weg zu Oligocyclopentadienyl‐Liganden: Synthese und erste Reaktionen der beiden isomeren Tercyclopentadienyle und ihrer Übergangsmetallkomplexe

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Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30

Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30