TY - JOUR
T1 - Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand
AU - Sharninghausen, Liam S.
AU - Sinha, Shashi Bhushan
AU - Shopov, Dimitar Y.
AU - Mercado, Brandon Q.
AU - Balcells, David
AU - Brudvig, Gary W.
AU - Crabtree, Robert H.
N1 - Funding Information:
This work (S.B.S., D.Y.S. and L.S.S.) was supported the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under Award Number DE-SC0001059 as part of the Argonne-Northwestern Solar Energy Research (ANSER) Energy Frontier Research Center (spectroscopy and characterization) and under Award Number DEFG02-07ER15909 (synthesis). D.B. was supported by the Research Council of Norway through a Centre of Excellence grant (Grant No. 179568/V30) and the Norwegian Supercomputing Program (NOTUR) through a grant for computing time (Grant No. NN4654K). D.B. also acknowledges the EU REA for a Marie Curie Fellowship (Grant CompuWOC/618303). Min Li and Zishan Wu at the Yale Materials Characterization Core are acknowledged for collection of XPS data.
PY - 2017/10/9
Y1 - 2017/10/9
N2 - We have prepared and fully characterized two isomers of [IrIV(dpyp)2] (dpyp=meso-2,4-di(2-pyridinyl)-2,4-pentanediolate). These complexes can cleanly oxidize to [IrV(dpyp)2]+, which to our knowledge represent the first mononuclear coordination complexes of IrV in an N,O-donor environment. One isomer has been fully characterized in the IrV state, including by X-ray crystallography, XPS, and DFT calculations, all of which confirm metal-centered oxidation. The unprecedented stability of these IrV 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.
AB - We have prepared and fully characterized two isomers of [IrIV(dpyp)2] (dpyp=meso-2,4-di(2-pyridinyl)-2,4-pentanediolate). These complexes can cleanly oxidize to [IrV(dpyp)2]+, which to our knowledge represent the first mononuclear coordination complexes of IrV in an N,O-donor environment. One isomer has been fully characterized in the IrV state, including by X-ray crystallography, XPS, and DFT calculations, all of which confirm metal-centered oxidation. The unprecedented stability of these IrV 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.
KW - alkoxide ligands
KW - computational chemistry
KW - high oxidation state
KW - iridium(V)
KW - redox chemistry
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U2 - 10.1002/anie.201707593
DO - 10.1002/anie.201707593
M3 - Article
C2 - 28815915
AN - SCOPUS:85028828813
VL - 56
SP - 13047
EP - 13051
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 42
ER -