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Verfasst von:Stoll, Michael E. [VerfasserIn]   i
 Lovelace, Sherri R. [VerfasserIn]   i
 Geiger, William E. [VerfasserIn]   i
 Schimanke, Holger [VerfasserIn]   i
 Hyla-Kryspin, Isabella [VerfasserIn]   i
 Gleiter, Rolf [VerfasserIn]   i
Titel:Transannular effects in dicobalta-superphane complexes on the mixed-valence class II/class III interface
Titelzusatz:distinguishing between spin and charge delocalization by electrochemistry, spectroscopy, and ab initio calculations
Verf.angabe:Michael E. Stoll, Sherri R. Lovelace, William E. Geiger, Holger Schimanke, Isabella Hyla-Kryspin, and Rolf Gleiter
E-Jahr:1999
Jahr:09/24/1999
Umfang:9 S.
Fussnoten:Gesehen am 30.10.2020
Titel Quelle:Enthalten in: American Chemical SocietyJournal of the American Chemical Society
Ort Quelle:Washington, DC : American Chemical Society, 1879
Jahr Quelle:1999
Band/Heft Quelle:121(1999), 40, Seite 9343-9351
ISSN Quelle:1520-5126
Abstract:The oxidative electron-transfer properties of several superphane complexes consisting of cyclopentadienylcobalt cyclobutadiene moieties linked by either three (compounds 1 and 4) or five (compounds 2 and 5) bridging methylene groups have been studied by experimental and theoretical methods. In both cases two separate one-electron oxidations are found. The mixed-valent monocations of the (−CH2−)5-bridged complexes are valence-trapped with very weak interactions between metal centers. The (−CH2−)3 complexes, however, have strong interactions between the two molecular halves. The intervalence transfer (IT) band of 1+ has characteristics of both class II (localized) and class III (delocalized) behavior, but the IR spectra of carboxy-labeled 4+ clearly establish trapped valence for the monocations of the propano-bridged systems. Photoelectron spectra and ab initio calculations at the UHF level show that, in the ground electronic state, 1+ has a half-filled orbital (i.e., electron spin) that is essentially localized in one Co dxy, orbital, but that the charges on the two metals are unequal owing to inductive electronic effects which give unequal electron flow from the ligands to the two metal centers. Calculations and IR (carbonyl) spectral shifts suggest about a 70:30 charge ratio between the two metal centers in 1+ and 4+, whereas both spin and charge localization is virtually complete in the pentano-bridged complexes 2+ and 5+. The intervalence transition in 1+ is proposed to proceed through a “hole”-transfer process mediated by a π-cyclobutadiene MO, ultimately involving a through-bond transannular mechanism.
DOI:doi:10.1021/ja9914792
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

Volltext ; Verlag: https://doi.org/10.1021/ja9914792
 Volltext: https://pubs.acs.org/doi/10.1021/ja9914792
 DOI: https://doi.org/10.1021/ja9914792
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:1737471604
Verknüpfungen:→ Zeitschrift

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