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References (10)
-
F. Nief, F. Mathey (1991)
New reactivity of phosphirenes (phosphacyclopropenes). synthesis of allenylphosphines and of functional phosphirenes.Tetrahedron, 47
-
G. Martin, E. Ocando-Mavárez (1991)
First 1‐phospha‐1,3‐dienes unsubstituted in the carbon chain by pyrolysis of diallylphosphines: A novel route to the phosphorus—carbon double bondHeteroatom Chemistry, 2
-
R. Loncharich, K. Houk (1987)
Transition structures of ene reactions of ethylene and formaldehyde with propeneJournal of the American Chemical Society, 109
-
M. Dewar, E. Zoebisch, Eamonn Healy, J. Stewart (1985)
Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular modelJournal of the American Chemical Society, 107
-
M. Dewar (1984)
Multibond reactions cannot normally be synchronousJournal of the American Chemical Society, 106
-
G. Martin, E. Ocando-Mavárez, A. Osorio, M. Laya, M. Canestrari (1992)
Gas phase thermolysis of allylphosphines, kinetic studyHeteroatom Chemistry, 3
-
M. Dewar, G. Ford (1977)
Thermal decarboxylation of but-3-enoic acid. MINDO/3 calculations of activation parameters and primary kinetic isotope effectsJournal of the American Chemical Society, 99
-
M. Mulcahy, Dj Williams (1961)
A Stirred-Flow Reactor for Investigating the Kinetics of Gaseous Reactions: Application to the Decomposition of Di-t-butyl PeroxideAustralian Journal of Chemistry, 14
-
F. Hartley (1990)
The Chemistry of Organophosphorus Compounds -
R. Appel, F. Knoch, Holger Kunze (1984)
Niederkoordinierte Phosphor‐Verbindungen, 281). MonophosphabutadieneChemische Berichte, 117
- Publisher
- Wiley
- Copyright
- Copyright © 1997 Wiley Subscription Services
- ISSN
- 1042-7163
- eISSN
- 1098-1071
- DOI
- 10.1002/(SICI)1098-1071(1997)8:2<97::AID-HC1>3.0.CO;2-#
- Publisher site
- See Article on Publisher Site
Abstract
Diallyltetramethylpiperidinophosphine 1, diallyldiisopropylaminophosphine 2, and diallylmesitylphosphine 3 were pyrolyzed in a stirred flow reactor over the temperature range 400–450°C, using toluene as carrier gas, producing, in all cases, mixtures of phosphorus‐containing products. The pyrolysis of 1 produced 1‐tetramethylpiperidino‐1‐phosphabutadiene, in addition to a mixture of phosphines and polyphosphines. Compound 2 produced the azadiphosphole 4, the phosphinine 5, allylphosphine, and diisopropylaminophosphine as major phosphorated products. The pyrolysis of 3 produced a mixture of phosphines and polyphosphines. The complex mixture generated by the three diallylphosphines indicates the formation of free radicals during their pyrolyses. AM1 calculations on the transition state of an expected retroenetype propene elimination reaction showed that, due to the phosphaalkene character of the transition state, the structure of the latter is very rigid and sensitive to steric effects. Steric hindrance of the substituents on the phosphorus atom compels the molecule to distort the half‐chair transition structure, causing a rise in the activation energy to values in the range of a homolytic P(SINGLE BOND)C bond dissociation energy. © 1997 John Wiley & Sons, Inc.
Journal
Heteroatom Chemistry – Wiley
Published: Jan 1, 1997