Intermolecular hydrogen transfer in unsaturated hydrocarbons induced by dimeric titanocene

1983 ◽  
Vol 48 (10) ◽  
pp. 2924-2936 ◽  
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.

Radikalionen, 61 [1, 2]Dialkylamino-substituierte Acetylene und Allene:Ionisation, Oxidation und AlCl3-katalysierte Wasserstoffübertragung / Radical Ions, 61 [1, 2]Dialkylamino-substituted Acetylenes and Allenes:Ionisation, Oxidation and AlCl3-Catalyzed Hydrogen Transfer

1984 ◽  
Vol 39 (6) ◽  
pp. 763-770 ◽  
Author(s):  
Hans Bock ◽  
Wolfgang Kaim ◽  
Mitsuo Kira ◽  
Louis Réné ◽  
Heinz-Günther Viehe
Keyword(s):  
Radical Cation ◽  
Hydrogen Transfer ◽  
Radical Cations ◽  
Esr Spectra ◽  
Ionization Potentials ◽  
Radical Ions ◽  
Substituted Acetylenes

AbstractThe photoelectron (PE) spectra of bis(dialkylamino) acetylenes R2N-C≡C-NR2 and of tetrakis(dialkylamino) allenes (R2N)2C=C=C(NR2)2 with R = CH3, C2H5 exhibit characteristic ionization patterns which are assigned to π radical cation states of the two molecular halves twisted against each other. The low first ionization potentials between 7.0 eV and 7.7 eV stimu­lated attempts to oxidize using AlCl3 in H2CCl2 or D2CCl2. The hyperfine structured ESR spectra observed can be unequivocally assigned to the ethylene radical cations R2N-HC=CH -NR2˙⊕ which are formed from the obviously non-persistent species R2N-C≡C-NR2˙⊕ via a hydrogen transfer. During the oxidation of the dialkylamino-substituted allenes no paramagnetic intermedi­ates could be detected, presumably due to a rapid dimerisation of the allene radical cation (R2N)2C=C=C(NR2)2˙⊕.

A study of intermolecular hydrogen transfer from naphthenes to 1-hexene over zeolite catalysts

2016 ◽  
Vol 516 ◽  
pp. 153-159 ◽  
Author(s):  
O.V. Potapenko ◽  
V.P. Doronin ◽  
T.P. Sorokina ◽  
O.V. Krol ◽  
V.A. Likholobov
Keyword(s):  
Hydrogen Transfer ◽  
Zeolite Catalysts ◽  
Intermolecular Hydrogen Transfer

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

2016 ◽  
Vol 18 (10) ◽  
pp. 7093-7099 ◽  
Author(s):  
Qiong Wu ◽  
Weihua Zhu ◽  
Heming Xiao
Keyword(s):  
Hydrogen Transfer ◽  
Bond Breaking ◽  
Cooperative Effects ◽  
Decomposition Reactions ◽  
Different Temperatures ◽  
Intermolecular Hydrogen Transfer ◽  
Subsequent Decomposition

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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