Publikationstyp: | Beitrag in wissenschaftlicher Zeitschrift |
Art der Begutachtung: | Peer review (Publikation) |
Titel: | Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium biaryl formation via cationic pincer-type PdIV intermediates |
Autor/-in: | Gerber, Roman Blacque, Olivier Frech Nabold, Christian M. |
DOI: | 10.1039/c1dt10398a |
Erschienen in: | Dalton Transactions |
Band(Heft): | 40 |
Heft: | 35 |
Seite(n): | 8996 |
Seiten bis: | 9003 |
Erscheinungsdatum: | 2011 |
Verlag / Hrsg. Institution: | Royal Society of Chemistry |
ISSN: | 1477-9226 1477-9234 |
Sprache: | Englisch |
Fachgebiet (DDC): | 540: Chemie |
Zusammenfassung: | The aliphatic, phosphine-based pincer complex [(C(10)H(13)-1,3-(CH(2)P(Cy(2))(2))Pd(Cl)] (1) is a highly active Negishi catalyst, enable to quantitatively couple various electronically activated, non-activated, deactivated, sterically hindered and functionalized aryl bromides with various diarylzinc reagents within short reaction times and low catalyst loadings. Experimental observations strongly indicate that a molecular mechanism is operative with initial chloride dissociation of 1 and formation of the cationic T-shaped 14e(-) complex [(C(10)H(13)-1,3-(CH(2)P(C(6)H(11))(2))(2))Pd](+) (B), which undergoes oxidative addition of an aryl bromide (Ar'Br) to yield the cationic, penta-coordinated aryl bromide pincer complexes of type [(C(10)H(13)-1,3-(CH(2)P(Cy(2))(2))Pd(Br)(aryl')](+) (C) with the metal center in the oxidation state of +IV and the aryl unit in cis position relative to the aliphatic pincer core. Subsequent transmetalation with Zn(aryl)(2) result in the cationic diaryl pincer complexes of type [(C(10)H(13)-1,3-(CH(2)P(Cy(2))(2))Pd(aryl)(aryl')](+) (D), which reductively eliminate the coupling products, thereby regenerating the catalyst. The neutral square planar aryl pincer complex--a possible key intermediate in the catalytic cycle--was found to be reversibly formed in the reaction mixture but is not involved in the catalytic mechanism. Similarly, palladium nanoparticles as the catalytically active form of 1 could have been excluded. |
URI: | https://digitalcollection.zhaw.ch/handle/11475/10464 |
Volltext Version: | Publizierte Version |
Lizenz (gemäss Verlagsvertrag): | Lizenz gemäss Verlagsvertrag |
Departement: | Life Sciences und Facility Management |
Enthalten in den Sammlungen: | Publikationen Life Sciences und Facility Management |
Dateien zu dieser Ressource:
Es gibt keine Dateien zu dieser Ressource.
Zur Langanzeige
Gerber, R., Blacque, O., & Frech Nabold, C. M. (2011). Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium biaryl formation via cationic pincer-type PdIV intermediates. Dalton Transactions, 40(35), 8996–9003. https://doi.org/10.1039/c1dt10398a
Gerber, R., Blacque, O. and Frech Nabold, C.M. (2011) ‘Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium biaryl formation via cationic pincer-type PdIV intermediates’, Dalton Transactions, 40(35), pp. 8996–9003. Available at: https://doi.org/10.1039/c1dt10398a.
R. Gerber, O. Blacque, and C. M. Frech Nabold, “Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium biaryl formation via cationic pincer-type PdIV intermediates,” Dalton Transactions, vol. 40, no. 35, pp. 8996–9003, 2011, doi: 10.1039/c1dt10398a.
GERBER, Roman, Olivier BLACQUE und Christian M. FRECH NABOLD, 2011. Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium biaryl formation via cationic pincer-type PdIV intermediates. Dalton Transactions. 2011. Bd. 40, Nr. 35, S. 8996–9003. DOI 10.1039/c1dt10398a
Gerber, Roman, Olivier Blacque, and Christian M. Frech Nabold. 2011. “Negishi Cross-Coupling Reaction Catalyzed by an Aliphatic, Phosphine Based Pincer Complex of Palladium Biaryl Formation via Cationic Pincer-Type PdIV Intermediates.” Dalton Transactions 40 (35): 8996–9003. https://doi.org/10.1039/c1dt10398a.
Gerber, Roman, et al. “Negishi Cross-Coupling Reaction Catalyzed by an Aliphatic, Phosphine Based Pincer Complex of Palladium Biaryl Formation via Cationic Pincer-Type PdIV Intermediates.” Dalton Transactions, vol. 40, no. 35, 2011, pp. 8996–9003, https://doi.org/10.1039/c1dt10398a.
Alle Ressourcen in diesem Repository sind urheberrechtlich geschützt, soweit nicht anderweitig angezeigt.