Gas-phase thermolysis of diallyl(4-fluorophenyl) and allyl(t-butylamino)phenyl phosphines
✍ Scribed by Edgar Ocando-Mavarez; Gonzalo Martin; Avelino Andrade
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 168 KB
- Volume
- 8
- Category
- Article
- ISSN
- 1042-7163
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✦ Synopsis
Dially(4-fluorophenyl)phosphine and allyl(t-butylamino)phenylphosphine were pyrolyzed in a stirredflow reactor at 340-420ЊC/9-19 Torr, using toluene as carrier gas. The primary reaction products were propene, 1-(4-fluorophenyl)-1-phosphabutadiene, and 1phenyl-2-t-butyliminophosphine. The phosphoruscontaining products gave rise to [4 ם 2] and [2 ם 2] cycloaddition products, respectively. The consumption of these phosphines showed first-order kinetics, with the rate coefficients following the Arrhenius equations: Dially(4-fluorophenyl)phosphine: 1מ 9 . 0 0 ע 0.32 k(s ) ס 10 exp 221מ( ע 4 kJ/mol RT) Allyl(t-butylamino)phenylphosphine: 1מ 9 . 0 4 ע 0.25 k(s ) ס 10 exp 311מ( ע 3 kJ/mol RT)
The results support a six-center cyclic transition-state unimolecular elimination reaction mechanism for both reactants.