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Issue 13, 2010
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Heterolytic splitting of H–X bonds at a cationic (PNP)Pd center

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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 = NH2, PCy2, 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]+.

Graphical abstract: Heterolytic splitting of H–X bonds at a cationic (PNP)Pd center

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Supplementary files

Article information


Submitted
02 Dec 2009
Accepted
02 Feb 2010
First published
03 Mar 2010

Dalton Trans., 2010,39, 3195-3202
Article type
Paper

Heterolytic splitting of H–X bonds at a cationic (PNP)Pd center

L. C. Gregor, C. Chen, C. M. Fafard, L. Fan, C. Guo, B. M. Foxman, D. G. Gusev and O. V. Ozerov, Dalton Trans., 2010, 39, 3195
DOI: 10.1039/B925265G

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