Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex

Xiaochen Cai, Subhojit Majumdar, George Charles Fortman, Catherine S.J. Cazin, Alexandra Martha Zoya Slawin, Charles Lhermitte, Rajeev Prabhakar, Meaghan E. Germain, Taryn Palluccio, Steven Patrick Nolan, Elena V. Rybak-Akimova, Manuel Temprado, Burjor Captain, Carl D. Hoff

Research output: Contribution to journalArticlepeer-review

50 Citations (Scopus)

Abstract

The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR3) complexes with O-2 has been examined. Stopped-flow kinetic studies show that O-2 binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))-(eta(2)-O-2)] occurs in a rapid, second-order process. The enthalpy of O-2 binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(eta(2)-O-2)] but to paramagnetic trans-[(Pd(IPr)(2)(eta(1)-O-2)(2)], which has been fully characterized. Computational studies addressing the energetics of O-2 binding have been performed and provide insight into reactivity changes as steric pressure is increased.

Original languageEnglish
Pages (from-to)1290-1293
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number5
DOIs
Publication statusPublished - 9 Feb 2011

Keywords

  • MOLECULAR-OXYGEN
  • ORGANIC-CHEMICALS
  • PHOSPHINE-LIGANDS
  • AEROBIC OXIDATION
  • HYDRIDE BOND
  • DIOXYGEN
  • CATALYSIS
  • SYSTEM
  • PEROXO
  • HYDROPEROXIDE

Fingerprint

Dive into the research topics of 'Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex'. Together they form a unique fingerprint.

Cite this