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A Terminal Iridium Oxo Complex with a Triplet Ground State
Author(s) -
Delony Daniel,
Kinauer Markus,
Diefenbach Martin,
Demeshko Serhiy,
Würtele Christian,
Holthausen Max C.,
Schneider Sven
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201905325
Subject(s) - iridium , chemistry , thermochemistry , bond dissociation energy , dissociation (chemistry) , hydrogen atom abstraction , delocalized electron , photochemistry , moiety , hydrogen atom , bond length , homonuclear molecule , computational chemistry , crystallography , molecule , hydrogen , stereochemistry , catalysis , crystal structure , organic chemistry , alkyl
Abstract A terminal iridium oxo complex with an open‐shell ( S =1) ground state was isolated upon hydrogen atom transfer (HAT) from the respective iridium(II) hydroxide. Electronic structure examinations support large spin delocalization to the oxygen atom. Selected oxo transfer reactions indicate the ambiphilic reactivity of the iridium oxo moiety. Calorimetric and computational examinations of the HAT revealed a bond dissociation free energy for the IrO−H bond that is sufficient for hydrogen atom abstraction towards C−H bonds and small contributions from entropy and spin–orbit coupling to the HAT thermochemistry.