Stable cis dialkyldiazenes (azoalkanes): cis-di-1-adamantyldiazene and cis-di-1-norbornyldiazene

Engel, Paul S.; Melaugh, Robert A.; Page, Matthew A.; Szilagyi, Sandor; Timberlake, Jack W.

doi:10.1021/ja00423a058

Cited by 11 publications

(1 citation statement)

References 2 publications

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“…Part I: [2]. and purified at room temperature without isomerization [4] [6]. Thermal cis + trans isomerization of 1 proceeds at 9l"with a half-life time of 1 h [7].…”

Section: Cis-1 Trans -1mentioning

confidence: 99%

Electron‐Transfer‐Catalyzed cis → trans Isomerization of 1,1′‐Azonorborane. Prototype of a reversible two‐stage storage system

Gescheidt

Lamprecht

Heınze

et al. 1992

Helvetica Chimica Acta

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~~~~ ~ ~ESR and cyclic voltammetry investigations show that isomerization of the radical cation of cis-1,l'-azonorbornane (cis-1) to the trans-radical ion proceeds too fast in solution for direct investigation of the cis-radical ion even at -78". The facile isomerization of the radical cation is in agreement with PM3 calculations proposing an activation barrier of only 17 kJ/mol. As a consequence, quantitative cis + trans isomerization of 1,l'-azonorbornane can effectively be accomplished by addition of catalytic amounts of one-electron oxidants. This is the first evidence for a radical-cation-catalyzed cis -+ frans isomerization of azo compounds.

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“…Part I: [2]. and purified at room temperature without isomerization [4] [6]. Thermal cis + trans isomerization of 1 proceeds at 9l"with a half-life time of 1 h [7].…”

Section: Cis-1 Trans -1mentioning

confidence: 99%

Electron‐Transfer‐Catalyzed cis → trans Isomerization of 1,1′‐Azonorborane. Prototype of a reversible two‐stage storage system

Gescheidt

Lamprecht

Heınze

et al. 1992

Helvetica Chimica Acta

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Thermochemistry of amidines and related compounds

Pihlaja

1991

Amidines and Imidates (1991)

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Aliphatische Azoverbindungen, XIII: cis‐ und trans‐1‐Azonorbornan

et al. 1981

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Die Isomerisierungsgeschwindigkeit von cis-in iruns-1-Azonorbornan (1) folgt bei 96.6"C linear dem Polaritatsparameter E : ' in verschiedenen aprotischen Losungsmitteln. Die geringe Steigung -0.034 dieser Korrelation deutet auf einen theoretisch vorgeschlagenen einfachen Inversionsmechanismus. In protischen Losungsrnitteln verlauft die Isomerisierung vie1 schneller, wofiir ein durch H-Brijcken begiinstigter Rotationsmechanismus moglich gehalten wird. Reaktionsenthalpie und Aktivierungsparameter der cis-rrans-Isomerisierung und die Aktivierungsparameter der Thermolyse von trans-1-Azonorbornan gestatten die Aufstellung eines vollstandigen Enthalpiediagramms. Die Struktur von cis-1 wurde durch Rontgenanalyse bei -60°C bestimmt. Die starke Winkeldeformation und der normale NN-Abstand im Kristall werden durch Kraft feldrechnungen richtig wiedergegeben. Aliphatic Azo Compounds, XI11 cisand frans-I-AzonorbornaneThe rates of isomerisation of cis-1-azonorbornane to the trans-isomer at 96.6"C in a series of aprotic solvents follow a linear correlation with E:' . The small slope of this correlation -0.034 argues for isomerisation via semilinearisation in agreement with theory. In protic solvents the isomerisation proceeds faster possibly due to a faster isomerisation by bond rotation which could be favoured by H-bonding. The heat and the activation parameters of the isomerisation and the activation parameters of thermal decomposition of iruns-1-azonorbornane allow the construction of a complete enthalpy diagram of this system. The structure of cis-t-azonorbornane was determined by X-ray analysis at -60°C. The observed angle deformations and the normal NNbond lengths are reproduced by force field calculations.cis-und trans-1-Azonorbornan (cis-1 und iruns-1) nehmen unter den aliphatischen Azoverbindungen Sonderstellungen ein 2).Das iruns-Isomere ist, wegen der hohen Spannung der bei der Thermolyse entstehenden 1-Norbornylradikale, eines der stabilsten rrans-reri-Azoalkane3.4J. Das cis-Isomere5j ist, neben cis-1-Azobicyclo[Z.l .llhexan2) das einzige kristallin isolierte cis-teri-Azoalkan. Im Gegensatz zu ande-Chem. Ber. 114(1981)

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Stable cis dialkyldiazenes (azoalkanes): cis-di-1-adamantyldiazene and cis-di-1-norbornyldiazene

Cited by 11 publications

References 2 publications

Electron‐Transfer‐Catalyzed cis → trans Isomerization of 1,1′‐Azonorborane. Prototype of a reversible two‐stage storage system

Electron‐Transfer‐Catalyzed cis → trans Isomerization of 1,1′‐Azonorborane. Prototype of a reversible two‐stage storage system

Thermochemistry of amidines and related compounds

Aliphatische Azoverbindungen, XIII: cis‐ und trans‐1‐Azonorbornan

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