The renaissance in cyclooctatetraene chemistry

Paquette, Leo A.

doi:10.1016/0040-4020(75)80303-6

Cited by 142 publications

(41 citation statements)

References 375 publications

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“…The narrowness and the high intensity of the double-peaked component have been attributed to masing (13). The double-peaked component first appears at H36a (2.2 mm) and is seen down to H21a (0.45 mm)-the shortest wavelength submillimeter a line observable from the ground (2,(13)(14)(15)(16). Yet the optical and near-infrared a lines show no sign of lasing (17).…”

Section: \Jmentioning

confidence: 96%

Transition-State Spectroscopy of Cyclooctatetraene

Hrovat

Borden

et al. 1996

Science

261

284

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The 351-nanometer photoelectron spectrum of the planar cyclooctatetraene radical anion (COT·-) shows transitions to two electronic states of cyclooctatetraene (COT). These states correspond to the D4h 1A1g state, which is the transition state for COT ring inversion, and the D8h 3A2u state. The electron binding energy of the 1A1g transition state is 1.099 ± 0.010 electron volts, which is lower by 12.1 ± 0.3 kilocalories per mole than that of the 3A2u state. The photoelectron spectrum shows that the singlet lies well below the triplet in D8h COT and confirms ab initio predictions that the molecule violates Hund's rule. Vibrational structure is observed for both features and is readily assigned by use of a simple potential energy surface.

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Section: \Jmentioning

confidence: 96%

Transition-State Spectroscopy of Cyclooctatetraene

Hrovat

Borden

et al. 1996

Science

261

284

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“…X-ray structural data point to a nonequivalence of the cyclooctatetraene rings, only one of which is planar [115]. The dynamic NMR spectra [118] reveal fast degenerate interconversions XXXlIa ~ XXXlIb.…”

Section: Xxxlia Xxxlibmentioning

confidence: 97%

“…Probably the best studied is the .7r, .7r-metallotropy of .7r-complexes of cyclooctatetraene [95,115,116]. A simpler instance of metallotropic tautomerism of this type is represented by the degenerate tautomerism of allene iron tetracarbonyl complex [117].…”

Section: A N-transfersmentioning

confidence: 99%

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The Problem Of Tautomerism

Olekhnovich

Zhdanov

1988

Molecular Design of Tautomeric Compounds

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The term tautomerism (from raviathe same -and #fpOC; -part -was coined by Laar [3] in 1885. Laar interpreted tautomerism not as dynamic isomerism but as a possibility that one substance may combine properties of two or more isomers resulting from the fact that one of the groups, usually hydrogen, occupies an intermediate location between two or more possible positions. The development ofthe term tautomerism has been traced in [4,5].

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“…Data set 2, densitometer integrated Weissenberg and precession films, R = 0.087, gave the distances as 1.38 (4) and 1.48 (4) ]k. The present data set, R = 0.03, gives these distances as 1.405 (5) The chlorocyclooctatrienyl anion is symmetrically disposed toward the Pd atom, and it adopts a configuration which is unique for cyclooctatetraene derivatives. Cyclooctatetraene has been found in the tub, chair, planar, and multicyclic forms, but it has not been reported in the boat form displayed in this complex (Schr6der, 1965;Paquette, 1975), nor has this DI-g-CHLORO-BIS[4,6-r/-(1-CHLOROCYCLOOCTATRIENYL)]DIPALLADIUM (II) form been suggested as an intermediate in cyclooctatetraene reactions. [A very similar cyclooctadienyl form has been found in acetonylacetonato(cycloocta-2,4-dienyl)palladium (Churchill, 1966).]…”

Section: Di-g-ehloro-bis[46-r/-(l-chlorocyclooctatrienyl)]dipalladiumentioning

confidence: 99%