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Verfasst von:Tauchert, Michael E. [VerfasserIn]   i
 Warth, Daniel C. M. [VerfasserIn]   i
 Braun, Sebastian M. [VerfasserIn]   i
 Pundt-Gruber, Irene [VerfasserIn]   i
 Ziesak, Alexandra Sabrina [VerfasserIn]   i
 Rominger, Frank [VerfasserIn]   i
 Hofmann, Peter [VerfasserIn]   i
Titel:Highly efficient nickel-catalyzed 2-methyl-3-butenenitrile isomerization
Titelzusatz:applications and mechanistic studies employing the TTP ligand family
Verf.angabe:Michael E. Tauchert, Daniel C.M. Warth, Sebastian M. Braun, Irene Gruber, Alexandra Ziesak, Frank Rominger, and Peter Hofmann
E-Jahr:2011
Jahr:21 April 2011
Umfang:20 S.
Fussnoten:Gesehen am 26.10.2022
Titel Quelle:Enthalten in: Organometallics
Ort Quelle:Washington, DC : ACS Publ., 1982
Jahr Quelle:2011
Band/Heft Quelle:30(2011), 10, Seite 2790-2809
ISSN Quelle:1520-6041
Abstract:A series of sterically and electronically fine-tuned, chelating diphosphine ligands were synthesized. The ligands are analogues of Triptyphos (TTP, 1), all based upon a variably 9,10-two-carbon-bridged 9,10-dihydroanthracene scaffold. These new TTP-type ligands were employed in the Ni(0)-catalyzed isomerization of 2-methyl-3-butenenitrile (2M3BN), one of the key steps of industrial adiponitrile production by the DuPont process. The reaction showed a surprising preference for ligands bearing electron-donating substituents, such as methoxy or methyl groups, in the phenyl para position of the Ni-ligating PPh2 units. Octyltriptyphos (3) afforded the highest 2M3BN-isomerization turnover rate yet reported. A series of deuterium-labeling experiments was performed to investigate the possibility of an isomerization mechanism consisting of a cascade of de- and rehydrocyanation steps, which could be excluded. Using the ethano-bridged ligand 4, complex 16a (4-κP:κP′)Ni(η3-C4H7)CN (supposedly an intermediate of the 2M3BN-isomerization reaction) was isolated, and its solid-state structure was determined by X-ray diffraction analysis. The complete catalytic cycle of 2M3BN isomerization with ligand 4, as suggested by the available experimental evidence, was modeled using DFT methods.
DOI:doi:10.1021/om200164f
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: https://doi.org/10.1021/om200164f
 DOI: https://doi.org/10.1021/om200164f
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:182003156X
Verknüpfungen:→ Zeitschrift

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