Heterolytic splitting of H–X bonds at a cationic (PNP)Pd center
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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](+).
author list (cited authors)
Gregor, L. C., Chen, C., Fafard, C. M., Fan, L., Guo, C., Foxman, B. M., Gusev, D. G., & Ozerov, O. V.