Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 13047-13051 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 56 |
| Issue number | 42 |
| DOIs | |
| Publication status | Published - Oct 9 2017 |
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Keywords
- alkoxide ligands
- computational chemistry
- high oxidation state
- iridium(V)
- redox chemistry
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
Cite this
Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand. / Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y.; Mercado, Brandon Q.; Balcells, David; Brudvig, Gary W; Crabtree, Robert H.
In: Angewandte Chemie - International Edition, Vol. 56, No. 42, 09.10.2017, p. 13047-13051.Research output: Contribution to journal › Article
}
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.
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
UR - http://www.scopus.com/inward/record.url?scp=85028828813&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85028828813&partnerID=8YFLogxK
U2 - 10.1002/anie.201707593
DO - 10.1002/anie.201707593
M3 - Article
VL - 56
SP - 13047
EP - 13051
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 42
ER -