title: Heterolytic splitting of H-X bonds at a cationic (PNP)Pd center.
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](+).
authors.affiliation: Department of Chemistry, Brandeis University, 415 South Street, Waltham, MA 02454, USA.
authors.forename: Lauren C
authors.initials: LC
authors.lastname: Gregor
authors.forename: Chung-Hsing
authors.initials: CH
authors.lastname: Chen
authors.forename: Claudia M
authors.initials: CM
authors.lastname: Fafard
authors.forename: Lei
authors.initials: L
authors.lastname: Fan
authors.forename: Chengyun
authors.initials: C
authors.lastname: Guo
authors.forename: Bruce M
authors.initials: BM
authors.lastname: Foxman
authors.forename: Dmitry G
authors.initials: DG
authors.lastname: Gusev
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Ozerov