Studies of the reactions of group 8 transition-metal ions Fe/sup +/, Co/sup +/, and Ni/sup +/ with linear alkanes. Determination of reaction mechanisms and MC/sub n/H/sub 2n//sup +/ ion structures using Fourier transform mass spectrometry collision-induced dissociation

Journal Article · Wed Aug 10 00:00:00 EDT 1983 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00354a003· OSTI ID:7119477

Jacobson, D B; Freiser, B S

With use of Fourier transform mass spectrometry, the ion products resulting from the reactions of the group 8 transition-metal ions Fe/sup +/, Co/sup +/, and Ni/sup +/ with a variety of hydrocarbons were studied by both collision-induced dissociation and specific ion-molecule reactions. Evidence is provided for four unique MC/sub 4/H/sub 8//sup +/ structures. All three metal ions dehydrogenate linear alkanes larger than propane via initial insertion into C-C bonds resulting in the formation of bis(olefin)-metal ion complexes. In addition, Fe/sup +/ also dehydrogenates linear alkanes via initial insertion into C-H bonds, producing an olefin-metal ion complex. ..beta..-Hydride transfers are more facile for Co/sup +/ than either Fe/sup +/ or Ni/sup +/. Secondary ..beta..-hydride transfers are more facile than primary ..beta..-hydride transfers for both Co/sup +/ and Ni/sup +/; however, the reverse is observed for Fe/sup +/. Both Co/sup +/ and Ni/sup +/ are highly selective against insertion into terminal C-C bonds, with Fe/sup +/ showing considerably less selectivity. Formation of MC/sub 4/H/sub 6//sup +/ ions from linear alkanes larger than butane occurs via initial alkane loss producing a metal ion-butene complex followed by dehydrogenation.

• Research Organization: Purdue Univ., West Lafayette, IN
• DOE Contract Number: AC02-80ER10689
• OSTI ID: 7119477
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 105:16; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
CHEMICAL REACTIONS
COBALT COMPOUNDS
COLLISIONS
COMPARATIVE EVALUATIONS
DEHYDROGENATION
HYDROCARBONS
ION COLLISIONS
ION-MOLECULE COLLISIONS
IRON COMPOUNDS
MASS SPECTROMETERS
MEASURING INSTRUMENTS
MOLECULE COLLISIONS
NICKEL COMPOUNDS
ORGANIC COMPOUNDS
SPECTROMETERS
TRANSITION ELEMENT COMPOUNDS