| Online-Ressource |
Verfasst von: | Tauchert, Michael E. [VerfasserIn]  |
| Warth, Daniel C. M. [VerfasserIn]  |
| Braun, Sebastian M. [VerfasserIn]  |
| Pundt-Gruber, Irene [VerfasserIn]  |
| Ziesak, Alexandra Sabrina [VerfasserIn]  |
| Rominger, Frank [VerfasserIn]  |
| Hofmann, Peter [VerfasserIn]  |
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 |
Highly efficient nickel-catalyzed 2-methyl-3-butenenitrile isomerization / Tauchert, Michael E. [VerfasserIn]; 21 April 2011 (Online-Ressource)