Reactions of FeOH/sup +/ and CoOH/sup +/ with alkanes in the gas phase

Journal Article · Wed Sep 17 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00279a005· OSTI ID:5241192

Cassady, C J; Freiser, B S

The gas-phase reactions of FeOH/sup +/ and CoOH/sup +/ with aliphatic alkanes up to C/sub 6/H/sub 14/ were studied. As was the case in earlier studies on MH/sup +/ and MCH/sub 3//sup +/ (M = Fe, Co), FeOH/sup +/ is found to be less reactive than CoOH/sup +/. For aliphatic alkanes, CoOH/sup +/ reacts with species larger than ethane, while FeOH/sup +/ only reacts with branched alkanes and hexane. Following initial C-H insertion, H/sub 2/O loss dominates the FeOH/sup +/ reactions. For CoOH/sup +/, however, H/sub 2/O loss leads to an activated Co/sup +/-alkyl complex which decomposes further. In addition, dehydrogenation with no H/sub 2/O elimination also occurs in contrast to FeH/sup +/, CoH/sup +/, and CoCH/sub 3//sup +/ with alkanes, where complete loss of the initial ligand is seen. Initial C-C insertion is also a major pathway leading to M(OH)(alkene)/sup +/ species, and for FeOH/sup +/, pressure-dependent adduct formation is also observed with hexane and several branched alkanes. Both FeOH/sup +/ and CoOH/sup +/ react with cyclopropane and cyclobutane by initial C-C insertion. For cyclopentane and cyclohexane, CoOH/sup +/ reacts exclusively by C-H insertion, while FeOH/sup +/ is unreactive. As expected on the basis of thermodynamic calculations, the overall reactivity of MOH/sup +/ is intermediate to that of MH/sup +/ and MCH/sub 3//sup +/.

• Research Organization: Purdue Univ., West Lafayette, IN
• DOE Contract Number: AC02-80ER10689
• OSTI ID: 5241192
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ADDUCTS
ALKANES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COBALT COMPOUNDS
COBALT HYDROXIDES
DATA
EXPERIMENTAL DATA
FLUIDS
GASES
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXIDES
INFORMATION
IRON COMPOUNDS
IRON HYDROXIDES
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
REACTION INTERMEDIATES
TRANSITION ELEMENT COMPOUNDS
YIELDS