Cooperative effects of different temperatures and pressures on the initial and subsequent decomposition reactions of the nitrogen-rich energetic crystal 3,3′-dinitroamino-4,4′-azoxyfurazan

The initiation mechanisms of 3,3′-dinitroamino-4,4′-azoxyfurazan at different temperatures and pressures are bimolecular intermolecular hydrogen transfer and unimolecular N–NO2 bond breaking.

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Intermolecular hydrogen transfer in unsaturated hydrocarbons induced by dimeric titanocene

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19832924 ◽

1983 ◽

Vol 48 (10) ◽

pp. 2924-2936 ◽

Cited By ~ 5

Author(s):

Karel Mach ◽

Lidmila Petrusová ◽

Helena Antropiusová ◽

Vladimír Hanuš ◽

František Tureček ◽

...

Keyword(s):

Hydrogen Transfer ◽

Titanium Content ◽

Esr Spectra ◽

Stable Complex ◽

Catalytic Complex ◽

Substitution Reactions ◽

Unsaturated Hydrocarbons ◽

Linear Alkanes ◽

Saturated And Aromatic Hydrocarbons ◽

Intermolecular Hydrogen Transfer

μ-(η5 : η5-Fulvalene)-di-μ-hydrido-bis(η5-cyclopentadienyltitanium) and μ-(η5 : η5-fulvalene)-μ-chloro-μ-hydrido-bis(cyclopentadienyltitanium) form a thermally stable complex which catalyzes the intermolecular hydrogen transfer in unsaturated hydrocarbons, in addition to isomerizations and cyclizations. Cyclic hydrocarbons disproportionate under catalysis to saturated and aromatic hydrocarbons, while linear olefins yield predominantly linear alkanes and high molecular weight tar. The catalyst enables the hydrocarbon system to approach the thermodynamic equilibrium through a series of substitution reactions between alkyl- and allyltitanocene-like species and olefins and dienes. The catalytic complex was characterized by UV and ESR spectra. About one half of overall titanium content could be converted to mononuclear η3-allyltitanocene-like species, stable up to 400 °C. This exceptional thermal stability is ascribed to a firmly bound allyl containing ligand.

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Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

Canadian Journal of Chemistry ◽

10.1139/v77-505 ◽

1977 ◽

Vol 55 (20) ◽

pp. 3596-3601 ◽

Cited By ~ 13

Author(s):

Michael T. H. Liu ◽

Barry M. Jennings

Keyword(s):

Thermal Decomposition ◽

Kinetic Parameters ◽

Diazo Compounds ◽

First Order ◽

Temperature Range ◽

Decomposition Reactions ◽

Consecutive Reactions ◽

Rate Processes ◽

Subsequent Decomposition

The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80–130 °C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes.

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