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Hydrogenolysis of Dinuclear PCNR Ligated PdII μ-Hydroxides and Their Mononuclear PdII Hydroxide Analogues.

Wilson D BaileyAlexander S PhearmanLapo LuconiAndrea RossinDmitry G YakhvarovLucia D'AccoltiSarah E FlowersWerner KaminskyRichard A KempGiuliano GiambastianiKaren I Goldberg
Published in: Chemistry (Weinheim an der Bergstrasse, Germany) (2019)
The hydrogenolysis of mono- and dinuclear PdII hydroxides was investigated both experimentally and computationally. It was found that the dinuclear μ-hydroxide complexes {[(PCNR )Pd]2 (μ-OH)}(OTf) (PCNH =1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole; PCNMe =1-[3-[(di-tert-butylphosphino)methyl]phenyl]-5-methyl-1H-pyrazole) react with H2 to form the analogous dinuclear hydride species {[(PCNR )Pd]2 (μ-H)}(OTf). The dinuclear μ-hydride complexes were fully characterized, and are rare examples of structurally characterized unsupported singly bridged μ-H PdII dimers. The {[(PCNMe )Pd]2 (μ-OH)}(OTf) hydrogenolysis mechanism was investigated through experiments and computations. The hydrogenolysis of the mononuclear complex (PCNH )Pd-OH resulted in a mixed ligand dinuclear species [(PCNH )Pd](μ-H)[(PCC)Pd] (PCC=a dianionic version of PCNH bound through phosphorus P, aryl C, and pyrazole C atoms) generated from initial ligand "rollover" C-H activation. Further exposure to H2 yields the bisphosphine Pd0 complex Pd[(H)PCNH ]2 . When the ligand was protected at the pyrazole 5-position in the (PCNMe )Pd-OH complex, no hydride formed under the same conditions; the reaction proceeded directly to the bisphosphine Pd0 complex Pd[(H)PCNMe ]2 . Reaction mechanisms for the hydrogenolysis of the monomeric and dimeric hydroxides are proposed.
Keyphrases
  • molecular docking
  • mass spectrometry
  • risk assessment
  • molecular dynamics simulations