MECHANISMS OF HOT HYDROGEN ATOM DISPLACEMENT REACTIONS WITH ALKANES

Journal Article · Thu Jul 20 04:00:00 EDT 1961 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01475a002· OSTI ID:4843691

Urch, D; Wolfgang, R

BS> Recoil tritium from nuclear reaction was used as the source of hot hydrogen and iodine or oxygen served as scavengers to suppress interference from the minority of tritium atoms that reach thermal energies. 99.5% of the products may be accounted for by replacement of one or possibly two hydrogen atoms or alkyl groups by the incoming hydrcgen. The detailed prcduct spectrum provides strong support for a model of the mechanism in which the incoming hydrogen displaces another group directly, without forming any metastable intermediate. The point and direction of impact as well as the energy of the hot species is thus paramount in determining the course of the reaction. The greater tendency to break C--H rather than C --C bonds is due to the greater exposure of the former. Other details in product distribution may be explained similarly by variations in steric obstruction to certain modes of impact. Hydrogen atom abstraction appears to follow axial approach of the hot atom along the C--H bond axis; while displacement occurs (without Walden inversion) as a result of attack at larger angles to the bond axis. (auth)

• Research Organization: Yale Univ., New Haven
• Sponsoring Organization: USDOE
• NSA Number: NSA-15-027658
• OSTI ID: 4843691
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 83; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ALKANES
ATOMS
CHEMISTRY
DECOMPOSITION
DISTRIBUTION
HYDROGEN
IMPACT SHOCK
IODINE
NUCLEAR REACTIONS
OXYGEN
REACTION KINETICS
RECOILS
TRITIUM