Allylic Amination of Pd(II)-Allyl Complexes via High-Valent Pd Intermediates

Yung Ching Wang, Nigam P. Rath, Liviu M. Mirica

Research output: Contribution to journalArticlepeer-review

Abstract

Organometallic high-valent Pd(allyl) complexes have been recently proposed to act as intermediates in catalytic allylic functionalization reactions. While a few PdIV(η1-allyl) complexes have been isolated and characterized, PdIII(η3-allyl) or PdIII(η1-allyl) complexes have not been detected or isolated to date. Reported herein is the synthesis, characterization, and reactivity of a series of PdII(η3-allyl) complexes supported by the tetradentate pyridinophane ligands N,N′-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane (tBuN4) and N,N′-di-tert-methyl-2,11-diaza[3.3](2,6)pyridinophane (MeN4). These PdII(η3-allyl) complexes exhibit accessible oxidation potentials and upon oxidation generate PdIII(allyl) complexes that were characterized by electron paramagnetic resonance (EPR) spectroscopy. Interestingly, the [(MeN4)PdIII(η3-allyl)]2+ complex undergoes a rearrangement to the [(MeN4)PdIII(η1-allyl)]2+ species at low temperatures. Moreover, fast allylic amination occurred within 15 min at room temperature upon the reaction of [(MeN4)PdII(η3-allyl)]+ complexes with N-fluorobenzenesulfonimide (NFSI), and the C-N bond formation step is proposed to occur at the Pd(IV) oxidation state, likely via a PdIV(η1-allyl) intermediate.

Original languageEnglish (US)
Pages (from-to)2067-2076
Number of pages10
JournalOrganometallics
Volume41
Issue number15
DOIs
StatePublished - Aug 8 2022

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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