ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The Arrhenius parameters for the thermal decomposition of ferrocenyl azide in isooctane are A = (5.1 ± 1.4) × 1012 s-1 and Eact = 113.1 ± 0.9 (kJ mol-1) and the rate is relatively insensitive to solvent (isooctane, benzene, acetonitrile: 1:1.7:2.4). The results indicate a relatively nonpolar transition state which is considerably “tighter” than for a normal bond fission reaction. The Arrhenius parameters are comparable to those for aromatic azides and do not offer any support for anchimeric assistance by the iron atom. A kinetic scheme is presented which accounts for the observed products: Nitrogen, ferrocene, aminoferrocene, azoferrocene, and insoluble material. Rates of hydrogen abstraction by the intermediate ferrocenyl nitrene from cyclohexane, benzene, and acetonitrile are used to show that the nitrene is nucleophilic. © 1994 John Wiley & Sons, Inc.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550260605
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