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 noninnocent 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 via a hydrazido(2−)/isodiazene valence tautomerization.

Electronic Structures of an [Fe(NNR2)]+/0/– Redox Series: Ligand Noninnocence and Implications for Catalytic Nitrogen Fixation

“…At the same time, many M­(NNR 2 ) complexes, especially those of the late transition metals, have been characterized as adducts of the charge-neutral isodiazene (NNR 2 ) oxidation state . Valence isomerization between these two closed-shell configurationshydrazido(2−) and isodiazenehas also been proposed …”

Dreyfus‐Preis und Camille‐Dreyfus‐Teacher‐Scholar‐Preise 2019

“…Sie entwickeln ein markierungsfreies Superauflösungsverfahren für die nanoskopische Bildgebung von Zellen, sie ermitteln den Einfluss von Schwingungen als Triebkraft von Elektronentransferreaktionen, und sie nutzen plasmonische Nanomaterialien, um chemische Reaktionen zu beobachten und zu katalysieren. Frontiera war Koautorin einer Angewandte‐Chemie ‐Zuschrift über die Redoxeigenschaften einer terminalen Iridium‐Hydrazid‐Dreifachbindung …”

Dreyfus Prize and Camille Dreyfus Teacher‐Scholar Awards 2019

“…They develop a label‐free, super‐resolution imaging technique to monitor cells on the nanometer scale, determine the role of vibrations in driving electron‐transfer reactions, and use plasmonic nanomaterials to monitor and catalyze chemical reactions. Frontiera was coauthor of a Communication in Angewandte Chemie on a redox‐noninnocent terminal iridium–hydrazido triple bond …”