Reactions of group 8 transition-metal ions (Fe/sup +/, Co/sup +/, and Ni/sup +/) with cyclic hydrocarbons in the gas phase

Journal Article · Tue Dec 27 23:00:00 EST 1983 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00364a003· OSTI ID:6856580

Jacobson, D B; Freiser, B S

The gas-phase reactions of group 8 transition-metal ion (Fe/sup +/, Co/sup +/, and Ni/sup +/) with cyclic hydrocarbons were studied by Fourier transform mass spectrometry. Product structures were probed by using collision-induced dissociation (CID) and H/D exchanges. All three metal ions react with cyclobutane to generate ring-cleavage products exclusively. This is in contrast to reactions with cyclopentane and cyclohexane, where dehydrogenation dominates, producing cycloalkene- and cycloalkadiene-metal ion complexes. Bis(ethene)- metal ion complexes formed in secondary reactions, are shown not to be in equilibrium with metallacyclopentanes. Metallacyclopentanes decompose by symmetric ring cleavage, producing an ethene-metal ion complex, or by an initial 1,3-hydrogen shift, producing a linear butene complex which dehydrogenates, forming a butadiene-metal ion complex. Both Fe-c-C/sub 5/H/sub 6//sup +/ undergo six H/D exchanges with D/sub 2/. The rate constant for the first exchange is found to be about an order of magnitude faster than for the second exchange. Cycloalkadiene products of Fe/sup +/ and Co/sup +/ react rapidly with their corresponding cyclic-alkane analogues exclusively by multiple dehydrogenations. Cycloalkadiene products of Ni/sup +/, however, were found to be unreactive with cyclic alkanes. 5 figures, 3 tables.

• Research Organization: Purdue Univ., West Lafayette, IN
• DOE Contract Number: AC02-80ER10689
• OSTI ID: 6856580
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 105:26; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
ALKANES
ALKENES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COBALT
COBALT COMPLEXES
COMPLEXES
CYCLOALKANES
CYCLOALKENES
CYCLOHEXANE
DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
DIENES
ELECTROMAGNETIC RADIATION
ELEMENTS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
FLUIDS
GASES
HIGH VACUUM
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
IONS
IRON
IRON COMPLEXES
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LASER RADIATION
LIGHT NUCLEI
METALS
NICKEL
NICKEL COMPLEXES
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
POLYENES
PRESSURE DEPENDENCE
RADIATIONS
REACTION KINETICS
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
YIELDS