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![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Heterolytic splitting of H-X bonds at a cationic (PNP)Pd center
Lauren C Gregor1, Chung-Hsing Chen, Claudia M Fafard
1Department of Chemistry, Brandeis University, 415 South Street, Waltham, MA 02454, USA.
Abstract:
The (PNP)PdOTf complex is a suitable synthetic equivalent of the [(PNP)Pd](+) fragment in reactions with various HX substrates. The [(PNP)Pd](+) fragment either simply binds HX molecules as L-type ligands (X = NH(2), PCy(2), imidazolyl) or heterolytically splits the H-X bond to produce [(PN(H)P)Pd-X](+) (X = H, CCR, SR). DFT calculations analyze the relative energetics of the two outcomes and agree with the experimental data. Calculations also allow to assess the unobserved Pd(IV) isomer [(PNP)Pd(H)(2)](+) and validate its unfavourability with respect to the Pd(II) isomer [(PN(H)P)PdH](+).
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