Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

Adam J. Pearce, Alyssa A. Cassabaum, Grace E. Gast, Renee R. Frontiera, Ian A. Tonks

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

The synthesis of the first terminal Group 9 hydrazido(2-) complex, Cp*IrN(TMP) (6) (TMP=2,2,6,6-tetramethylpiperidine) is reported. Electronic structure and X-ray diffraction analysis indicate that this complex contains an Ir−N triple bond, similar to Bergman's seminal Cp*Ir(NtBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non-innocent reactivity owing to the presence of the Nβlone pair. Treatment of 6 with MeI results in electron transfer from Nβto Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally IrIIImetal center through a hydrazido(2−)/isodiazene valence tautomerization.

Original languageEnglish (US)
Pages (from-to)13169-13173
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number42
DOIs
StatePublished - 2016

Keywords

  • hydrazide ligands
  • iridium complexes
  • organometallic chemistry
  • redox non-innocence
  • triple bonds

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