Gas-phase reactions of Group VIII metal hydride ions (FeD+, CoD+, and NiD+) with hydrocarbons

Carlin, T. J.; Sallans, Larry; Cassady, Carolyn J.; Jacobson, D. B.; Freiser, Ben S.

doi:10.1021/ja00358a027

Cited by 68 publications

(32 citation statements)

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“…Although the electron affinity of hydrogen is much lower, the corresponding metal-hydride cations MH ϩ behave similar to the metal halides in several respects (42)(43)(44) …”

Section: Ligated Metal Cationsmentioning

confidence: 99%

Gas-phase activation of methane by ligated transition-metal cations

Schröder

Schwarz²

2008

Proc. Natl. Acad. Sci. U.S.A.

234

135

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Motivated by the search for ways of a more efficient usage of the large, unexploited resources of methane, recent progress in the gas-phase activation of methane by ligated transition-metal ions is discussed. Mass spectrometric experiments demonstrate that the ligands can crucially influence both reactivity and selectivity of transition-metal cations in bond-activation processes, and the most reactive species derive from combinations of transition metals with the electronegative elements fluorine, oxygen, and chlorine. Furthermore, the collected knowledge about intramolecular kinetic isotope effects associated with the activation of C-H(D) bonds of methane can be used to distinguish the nature of the bond activation as a mere hydrogen-abstraction, a metal-assisted mechanism or more complex reactions such as formation of insertion intermediates or -bond metathesis.bond activation ͉ kinetic isotope effects ͉ mass spectrometry

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“…Although the electron affinity of hydrogen is much lower, the corresponding metal-hydride cations MH ϩ behave similar to the metal halides in several respects (42)(43)(44) …”

Section: Ligated Metal Cationsmentioning

confidence: 99%

Gas-phase activation of methane by ligated transition-metal cations

Schröder

Schwarz²

2008

Proc. Natl. Acad. Sci. U.S.A.

234

135

View full text Add to dashboard Cite

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“…In contrast, at the theoretical level used all relevant stationary points are higher in energy for the singlet states as compared to their triplet electromers. A one-state scenario has also been reported for the related Fe(OCH 3 …”

mentioning

confidence: 66%

“…As our current experimental set-up does not permit an unambiguous structural characterization of the species involved in the Ni(C,H 3 . Two other minima have been located on the triplet surface.…”

mentioning

confidence: 96%

“…-The present experiments were performed with a VG BIO-Q mass spectrometer of QHQ configuration (Q: quadrupole, H: hexapole) equipped with an ESI source as described in details previously [8] [9]. In brief, the complexes having the elemental compositions Ni(C,H 3 …”

mentioning

confidence: 99%

“…As to the relevance of the computational findings, we can provide circumstantial experimental evidence for some of the predictions. For example, CID studies of massselected Ni(C,H 3 …”

mentioning

confidence: 99%

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Specific Processes and Scrambling in the Dehydrogenation of Ethane and the Degenerate Hydrogen Exchange in the Gas‐Phase Ion Chemistry of the Ni(C,H₃,O)⁺/C₂H₆ Couple

Schlangen

Schwarz

Schröder

2007

Helvetica Chimica Acta

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A mechanistically unprecedented situation characterizes the gas‐phase ion chemistry of Ni(C,H3,O)+ when reacted under thermal, single‐collision conditions with ethane. A dehydrogenation channel leading to Ni(C3,H7,O)+ is to 90% preceded by a complete loss of positional identity of all nine H‐atoms of the encounter complex (‘scrambling’), whereas ca. 10% of the reaction exhibit a selective CH bond activation of the alkane. In addition, a degenerate H exchange between ethane and the (C,H3,O) unit occurs as a side reaction, the mechanistic details of which remain unknown for the time being.

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The Gas‐Phase Chemistry of Transition‐Metal Ions with Organic Molecules

Allison¹

1986

Progress in Inorganic Chemistry

108

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Gas-phase reactions of Group VIII metal hydride ions (FeD+, CoD+, and NiD+) with hydrocarbons

Cited by 68 publications

References 0 publications

Gas-phase activation of methane by ligated transition-metal cations

Gas-phase activation of methane by ligated transition-metal cations

Specific Processes and Scrambling in the Dehydrogenation of Ethane and the Degenerate Hydrogen Exchange in the Gas‐Phase Ion Chemistry of the Ni(C,H₃,O)⁺/C₂H₆ Couple

The Gas‐Phase Chemistry of Transition‐Metal Ions with Organic Molecules

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Gas-phase reactions of Group VIII metal hydride ions (FeD+, CoD+, and NiD+) with hydrocarbons

Cited by 68 publications

References 0 publications

Gas-phase activation of methane by ligated transition-metal cations

Gas-phase activation of methane by ligated transition-metal cations

Specific Processes and Scrambling in the Dehydrogenation of Ethane and the Degenerate Hydrogen Exchange in the Gas‐Phase Ion Chemistry of the Ni(C,H3,O)+/C2H6 Couple

The Gas‐Phase Chemistry of Transition‐Metal Ions with Organic Molecules

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Specific Processes and Scrambling in the Dehydrogenation of Ethane and the Degenerate Hydrogen Exchange in the Gas‐Phase Ion Chemistry of the Ni(C,H₃,O)⁺/C₂H₆ Couple