Energy barrier by cyclopropylchlorocarbene rearrangement measured by direct observation of the carbene in laser flash spectroscopy

Journal Article · Thu Oct 19 00:00:00 EDT 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100358a007· OSTI ID:6738038

Liu, M T.H.; Bonneau, R ^[1]

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1. Universite de Bordeaux, Talence (France)

A transient absorption in the 250-265-nm range is assigned to cyclopropylchlorocarbene generated from the laser flash photolysis of 3-chloro-3-cyclopropyldiazirine. Confidence in this assignment was obtained from the following: (a) the decay of this absorption matches the growth of the pyridinium ylide: (b) the values for the rate constant for reaction of the carbene with 1-hexane obtained by monitoring the carbene at 250 nm and the ylide at 370 nm are similar. The kinetic parameters for the rearrangement of cyclopropylchlorocarbene to 1-chlorocyclobutene are log A = 11.1 and E{sub a} = 7.4 kcal/mol.

• OSTI ID: 6738038
• Journal Information: Journal of Physical Chemistry; (USA), Vol. 93:21; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBENES
PHOTOLYSIS
CHEMICAL REACTION KINETICS
DATA ANALYSIS
EXPERIMENTAL DATA
LASER SPECTROSCOPY
MEASURING INSTRUMENTS
MEASURING METHODS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
INFORMATION
KINETICS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
RADICALS
REACTION KINETICS
SPECTROSCOPY
400201* - Chemical & Physicochemical Properties