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Redox Non‐Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond
Author(s) -
Pearce Adam J.,
Cassabaum Alyssa A.,
Gast Grace E.,
Frontiera Renee R.,
Tonks Ian A.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607648
Subject(s) - iridium , chemistry , tautomer , lone pair , redox , valence (chemistry) , reactivity (psychology) , triple bond , hydride , metal , stereochemistry , medicinal chemistry , crystallography , photochemistry , double bond , polymer chemistry , molecule , inorganic chemistry , catalysis , organic chemistry , medicine , alternative medicine , pathology
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(N t Bu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non‐innocent reactivity owing to the presence of the N β lone pair. Treatment of 6 with MeI results in electron transfer from N β 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 Ir III metal center through a hydrazido(2−)/isodiazene valence tautomerization.