The Triethylenediamine Cation Radical

McKinney, Ted M.; Geske, David H.

doi:10.1021/ja01091a044

Cited by 74 publications

(31 citation statements)

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“…More importantly, the signal direction indicates a positive hyperfine coupling constant for the cyclopropane protons. This assignment rules out any delocalization of spin onto the tertiary cyclopropane carbons as in structure type 13 and is compatible 'The oxidation potential of dimethoxybenzene is 1.34 V vs. SCE (21), that of fluorene is 1.65 V vs. SCE (22).…”

Section: Norcarene Clerivativessupporting

confidence: 53%

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Radical cations of strained ring hydrocarbons. Cyclopropane derivatives

Roth¹,

Schilling²

1983

Can. J. Chem.

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Bell L[zbortrtorie.s, M~r r r r r~ H i l l . NJ 07974. U.S.A . Receivcd July 27, 1982This l~trper is tletlicnted to Professor Htrrry E . G L~I I I I~I I~ 011 the oc.ctr~ioll Of his 65th birth(1tly HEINZ D. ROTH and MARCIA L. MANION SCHILLING. Can. J. Chern. 61, 1027(1983.A series of radical cations has been generated from various cyclopropane derivatives by photoinitiated electron transfcr to chloranil. Nuclcar spin polarization effects observed during these reactions have been interpreted as evidence for the structure of these intermediates. Tri-and tetraalkylsubstituted cyclopropanes (1, 3. 4) form "trirnethylene" radical cations in which the most highly substituted carbon-carbon bond is broken (or weakened). Thc benzocyclopropanorbornene (12) forms a radical cation in which spin and charge are located in the benzenoid ring; the tertiary cyclopropane protons are coupled by a homohyperconjugative interaction; otherwise, the cyclopropane ring is unaffected. To the radical cation derived from bisrnethanoparacyclophane (17) a trirnethylene structure is assigned in which the benzylic carbons are pyramidal. Finally, benzonorcaradiene (20) forms a radical cation in which the two secondary-tertiary bonds are lengthened and in which the rnethylene group bears spin density. Chcrn. 61, 1027Chcrn. 61, (1983.On a produit une sCrie de cations radicalaires a partir de divers derives du cyclopropane en utilisant un transfert d'Clcctron photoinduit sur le chloranil. On a interprCtC les effets de polarisation de spin nucleaire observCs dans ces reactions cornrne une preuve de structure de ces interrnidiaires. Les cyclopropanes portant dcs substituants tri et titraalkylcs (1, 3, 4) forrnent des cations radicalaires "trirnCthylkne" dans lesquels la liaison carbone-carbone la plus substituCe est rornpue (ou affaiblie). Le benzocyclopropanorbornknc (12) forrne un cation radicalaire dans lequel le spin et la chargc sont IocalisCs dans le cycle benzenique; les protons tertiaires du cyclopropane sont couplts par une interaction hornohyperconjuguCe sans quoi le cycle cyclopropane n'est pas affect& Au cation radicalaire provenant du birnCthanoparacyclophane (17) on a attribuk une structure trirnkthylkne dans laquelle les carbones benzyliques sont pyrarnidaux. Finalcrnent le benzonorcaradi2ne (20) forrne un cation radicalaire dans lequel deux liaisons secondaire-tertiaires sont allongees et dans lequel le groupe rnkthylkne porte la densite de spin.[Traduit par le journal]For several years we have been interested in photoinitiated electron transfer reactions and have utilized chemically induced nuclear polarization (CIDNP) effects to gain an insight into the structure and reactivity of short-lived radical cations which can be generated in this type of reaction (1, 2). The CIDNP technique is based on the interpretation of greatly enhanced nmr signals in either absorption or emission, which may be observed during reactions proceeding via pairs of radicals or radical ions (3). According to the generally accepted radical pair theory the dir...

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Section: Norcarene Clerivativessupporting

confidence: 53%

“…The first structure is essentially a styrene radical cation in which charge and spin are delocalized over eight carbon atoms and in which the cyclopropane ring is unaffected (21). In the second structure, the 3"-3" cyclopropane bond is broken and charge and spin are delocalized over ten carbon atoms (22).…”

Section: Benzorzo~ca~adiet~ementioning

confidence: 99%

Radical cations of strained ring hydrocarbons. Cyclopropane derivatives

Roth¹,

Schilling²

1983

Can. J. Chem.

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“…The 1,4-diazabicyclo[2,2,2]octane is quasi-reversibly oxidized at 0.48 V under experimental conditions, and it is known that the relatively stable radical cation is formed during electrochemical oxidation process [18]. The electrolysis (0.58 V, Pt-working electrode) of the solution of Ph 3 Sb [4, (4), during 2 h leads to the appearance of new waves in cathode region ( Supplementary Fig.…”

Section: Air-free Conditionsmentioning

confidence: 99%

New morpholine- and piperazine-functionalized triphenylantimony(V) catecholates: The spectroscopic and electrochemical studies

Poddel’sky

Smolyaninov

Kurskii

et al. 2010

Journal of Organometallic Chemistry

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“…Triethylenediamine has an absorption band at long wavelengths (Amax 25 1 nm, E 1000) (20) which has been assigned to the interaction of the nonbonding pairs of electrons on the nitrogens through the carbon-carbon cr-bonds (19). Calculations show that the carbon-carbon cr-bond in triethylenediamine is weakened in the low-lying excited state ( 1 9~) .…”

Section: Discussionmentioning

confidence: 99%

Electronic Excited States of the Cyclic 1,4-Diaza-1,3-diene (Cyclic α-Diimine) System. Photochemical Reactions of 2H-Isoimidazole, 5,6-Dihydropyrazine, and 1,4-Diazepine Derivatives

Arnold¹,

Abraitys²,

McLeod³

1971

Can. J. Chem.

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The five-, six-, and seven-membered cyclic 1,4-diaza-l,3-dienes have been irradiated under a variety of conditions. The six-membered ring (dihydropyrazine) opens in a 6ne valence isomerization reaction. The resulting enediimine is stable at low temperatures and has been characterized (i.r.). Irradiation of 2,3,5,5-tetramethyl-5,6-dihydropyrazine (lb) results in formation of the enediimine 26 which reacts further to give the rearranged monomer 12 and/or dimers 13 depending upon the temperature. The fiveand seven-membered systems are stable to irradiation in inert solvents. However, irradiation of 2,2-dimethyl-4,5-diphenylisoimidazole (10h) in isopropyl alcohol gives the dihydroderivative 19 and in tetramethylethylene the one-to-one adduct 25.The U.V. spectrum of the six-membered ring (5,6-dihydropyrazine) is very different from that of the five-and seven-membered rings. The long wavelength maximum (ca. 350 nm) of the six-membered ring is attributed to a transition directly into an excited state common to the enediimine 2 (i.e., the excited state has a node between C-5 and -6 of the dihydropyrazine).

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The Triethylenediamine Cation Radical

Cited by 74 publications

References 0 publications

Radical cations of strained ring hydrocarbons. Cyclopropane derivatives

Radical cations of strained ring hydrocarbons. Cyclopropane derivatives

New morpholine- and piperazine-functionalized triphenylantimony(V) catecholates: The spectroscopic and electrochemical studies

Electronic Excited States of the Cyclic 1,4-Diaza-1,3-diene (Cyclic α-Diimine) System. Photochemical Reactions of 2H-Isoimidazole, 5,6-Dihydropyrazine, and 1,4-Diazepine Derivatives

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