title: Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2-) Triple Bond.
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.
authors.affiliation: Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
authors.forename: Adam J
authors.initials: AJ
authors.lastname: Pearce
authors.affiliation: Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
authors.forename: Alyssa A
authors.initials: AA
authors.lastname: Cassabaum
authors.affiliation: Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
authors.forename: Grace E
authors.initials: GE
authors.lastname: Gast
authors.affiliation: Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
authors.forename: Renee R
authors.initials: RR
authors.lastname: Frontiera
authors.affiliation: Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant St SE, Minneapolis, MN, 55455, USA. itonks@umn.edu.
authors.forename: Ian A
authors.initials: IA
authors.lastname: Tonks
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D006834:Hydrazines / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory
chemical_list: D056831:Coordination Complexes; D006834:Hydrazines; D007495:Iridium
keywords: hydrazide ligands; iridium complexes; organometallic chemistry; redox non-innocence; triple bonds