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Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O‐Donor Organic Ligand
Author(s) -
Sharninghausen Liam S.,
Sinha Shashi Bhushan,
Shopov Dimitar Y.,
Mercado Brandon Q.,
Balcells David,
Brudvig Gary W.,
Crabtree Robert H.
Publication year - 2017
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.201707593
Subject(s) - iridium , chemistry , ligand (biochemistry) , oxidation state , alkoxide , crystallography , x ray photoelectron spectroscopy , metal , catalysis , organic chemistry , biochemistry , receptor , physics , nuclear magnetic resonance
We have prepared and fully characterized two isomers of [Ir IV (dpyp) 2 ] (dpyp=meso‐2,4‐di(2‐pyridinyl)‐2,4‐pentanediolate). These complexes can cleanly oxidize to [Ir V (dpyp) 2 ] + , which to our knowledge represent the first mononuclear coordination complexes of Ir V in an N,O‐donor environment. One isomer has been fully characterized in the Ir V state, including by X‐ray crystallography, XPS, and DFT calculations, all of which confirm metal‐centered oxidation. The unprecedented stability of these Ir V complexes is ascribed to the exceptional donor strength of the ligands, their resistance to oxidative degradation, and the presence of four highly donor alkoxide groups in a plane, which breaks the degeneracy of the d‐orbitals and favors oxidation.