Nickel ions affect a highly specific 1,4-dehydrogenation of hydrocarbons in the gas phase: metallacycles are not involved

Journal Article · Wed Nov 17 04:00:00 EST 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00387a024· OSTI ID:5556269

Halle, L F ^[1]; Houriet, R; Kappes, M M; Staley, R H; Beauchamp, J L

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1. California Inst. of Tech., Pasadena

Reactions of singly charged atomic nickel ions with several linear alkanes have been studied using an ion beam apparatus and ion cyclotron resonance spectroscopy (ICR). Results using deuterated compounds indicate that dehydrogenation is an important reaction which proceeds via a highly specific 1,4 process. ICR studies of the subsequent reactions of the NiC/sub 4/H/sub 8//sup +/ ion formed from dehydrogenation of n-butane with Ni/sup +/ suggest that loss of H/sub 2/ occurs by oxidative addition to the internal carbon-carbon bond followed by a ..beta..-hydrogen transfer to the metal. This intermediate can then either reductively eliminate an alkane or abstract another ..beta.. hydrogen and eliminate H/sub 2/, forming what can be most simply described as a bisolefin complex. The major product from reaction of Ni/sup +/ with cyclopentanone is NiC/sub 4/H/sub 8//sup +/, probably a metallacycle, which reacts quite differently from the corresponding ion formed by dehydrogenation of n-butane.

• OSTI ID: 5556269
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:23; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
BEAMS
CHARGED PARTICLES
CHEMICAL ANALYSIS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DEHYDROGENATION
HYDROCARBONS
ION BEAMS
ION CYCLOTRON RESONANCE SPECTROSCOPY
ION SPECTROSCOPY
IONS
KINETICS
NICKEL IONS
ORGANIC COMPOUNDS
QUALITATIVE CHEMICAL ANALYSIS
QUANTITATIVE CHEMICAL ANALYSIS
REACTION KINETICS
SPECTROSCOPY