Reactions of FeCH/sub 3//sup +/ and CoCH/sub 3//sup +/ with cyclic hydrocarbons in the gas phase

Journal Article · Wed Jul 11 04:00:00 EDT 1984 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00326a003· OSTI ID:6507785

Jacobson, D B; Freiser, B S

The gas-phase reactions of FeCH/sub 3//sup +/ and CoCH/sub 3//sup +/ with cyclic hydrocarbons (C/sub 3/ through C/sub 6/) were studied. Both FeCH/sub 3//sup +/ and CoCH/sub 3//sup +/ react with cyclopropane and cyclobutane by cleavage of the ring. For cyclopropane, insertion into a C-C bond results in initial formation of an ethyl-ethene complex which is in rapid equilibrium with hydrido-bis(ethene) complex. Elimination of ethene then yields MC/sub 2/H/sub 5//sup +/ which appears to consist of a hydrido-ethene and an ethyl complex in equilibrium. Both FeCH/sub 3//sup +/ and CoCH/sub 3//sup +/ generate stable methyl-ethene complexes with cyclobutane. No reaction is observed for FeCH/sub 3//sup +/ with either cyclopentane or cyclohexane; however, CoCH/sub 3//sup +/ is reactive with retention of the integrity of the ring structures. A Co-c-C/sub 5/H/sub 7//sup +/ species is formed which undergoes two H/D exchanges with D/sub 2/. Co-c-C/sub 6/H/sub 7//sup +/ undergoes only one H/D exchange while no exchanges are seen for Fe-c-C/sub 6/H/sub 7//sup +/ with D/sub 2/. Products corresponding to protonated ferrocene and cobaltocene are generated and readily eliminate a hydrogen atom forming the respective metallocenes in high efficiency upon collisional activation. A lower limit of 84 and 66 kcal/mol is assigned to D/sup 0/ (Co/sup +/-c-C/sub 5/H/sub 5/) and D/sup 0/(Fe/sup +/-c-C/sub 5/H/sub 5/), respectively. D/sup 0/ = metal-allyl bond strength. 28 references, 2 figures.

• Research Organization: Purdue Univ., West Lafayette, IN
• DOE Contract Number: AC02-80ER10689
• OSTI ID: 6507785
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:14; 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)
ALKANES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPARATIVE EVALUATIONS
COMPLEXES
CYCLOALKANES
CYCLOHEXANE
DATA
EXPERIMENTAL DATA
FLUIDS
FOURIER TRANSFORM SPECTROMETERS
GASES
HYDROCARBONS
INFORMATION
ION CYCLOTRON RESONANCE SPECTROSCOPY
ION SPECTROSCOPY
IONS
IRON COMPLEXES
KINETICS
LIGANDS
MASS SPECTROSCOPY
MEASURING INSTRUMENTS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
SPECTROMETERS
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES