Deceptive similarities in the reactions of Fe/sup +/ and Co/sup +/ with linear nitriles in the gas phase

Journal Article · Wed Sep 16 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00253a013· OSTI ID:5975989

Lebrilla, C B; Drewello, T; Schwarz, H

The gas-phase reactions of the transition-metal ions Fe/sup +/ and Co/sup +/ with linear C(4)-C(12) nitriles are reported. In spite of an overall similar reactivity pattern, a more detailed analysis, based on the study of labeled nitriles, reveals distinct differences with regard to the mechanisms of elimination of alkenes and alkanes. For both metal ions, hydrogen and alkenes are generated from linear C(4)-C(12) nitriles, and the intermediates are formed via oxidative addition to terminal and internal C-H bonds. For the RCN/Fe/sup +/ system insertion in an internal C-H bond commences at position C(8) of the nitrile; for the analogous RCN/Co/sup +/ system, the oxidative addition to an internal C-H bond starts at position C(7) of the nitrile. Similarly, alkane formation is different for the two transition-metal ions. For RCN/Fe/sup +/ the generation of alkanes is observed for nitriles having at least eight carbon atoms; in contrast, the elimination of alkanes from RCN/Co/sup +/ is already observed for C(6) nitriles. Alkane elimination seems to follow the conventional mechanism (i.e., oxidative addition to a C-C bond, ..beta..-hydrogen transfer, and reductive elimination) for the RCN/Co/sup +/ system, whereas for the RCN/Fe/sup +/ complex there is an additional mechanism. This mechanism corresponds to the loss of H/sub 2/ from an internal position of the alkyl chain followed by the elimination of an alkene. Some possible origins of the different behavior of Fe/sup +/ vs. Co/sup +/ are discussed.

• Research Organization: Technische Universitaet Berlin, West Germany
• OSTI ID: 5975989
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
CATIONS
CHARGED PARTICLES
CHEMICAL BONDS
CHEMICAL REACTIONS
COBALT COMPOUNDS
DATA
ENERGY
EXPERIMENTAL DATA
FLUIDS
GASES
INFORMATION
IONS
IRON COMPOUNDS
LABELLING
MASS SPECTROSCOPY
NITRILES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REACTION INTERMEDIATES
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS