Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium biaryl formation via cationic pincer-type PdIV intermediates

Gerber, Roman; Blacque, Olivier; Frech Nabold, Christian M.

doi:10.1039/c1dt10398a

Publication type:	Article in scientific journal
Type of review:	Peer review (publication)
Title:	Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium biaryl formation via cationic pincer-type PdIV intermediates
Authors:	Gerber, Roman Blacque, Olivier Frech Nabold, Christian M.
DOI:	10.1039/c1dt10398a
Published in:	Dalton Transactions
Volume(Issue):	40
Issue:	35
Page(s):	8996
Pages to:	9003
Issue Date:	2011
Publisher / Ed. Institution:	Royal Society of Chemistry
ISSN:	1477-9226 1477-9234
Language:	English
Subject (DDC):	540: Chemistry
Abstract:	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
Fulltext version:	Published version
License (according to publishing contract):	Licence according to publishing contract
Departement:	Life Sciences and Facility Management
Appears in collections:	Publikationen Life Sciences und Facility Management

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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.