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Updated: Mar 14, 2026

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Redox Non-Innocent Behavior of a Terminal Iridium Hydrazido(2-) Triple Bond
Adam J Pearce1, Alyssa A Cassabaum1, Grace E Gast1
1Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
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(Nt Bu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non-innocent reactivity owing to the presence of the Nβ lone pair. Treatment of 6 with MeI results in electron transfer from Nβ to 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 IrIII metal center through a hydrazido(2-)/isodiazene valence tautomerization.
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