Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand

Liam S. Sharninghausen, Shashi Bhushan Sinha, Dimitar Y. Shopov, Brandon Q. Mercado, David Balcells, Gary W Brudvig, Robert H. Crabtree

Research output: Contribution to journalArticle

6 Citations (Scopus)

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 languageEnglish
Pages (from-to)13047-13051
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number42
DOIs
Publication statusPublished - Oct 9 2017

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Iridium
Coordination Complexes
Isomers
Ligands
Oxidation
X ray crystallography
Discrete Fourier transforms
X ray photoelectron spectroscopy
Metals
Degradation

Keywords

  • alkoxide ligands
  • computational chemistry
  • high oxidation state
  • iridium(V)
  • redox chemistry

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Sharninghausen, L. S., Sinha, S. B., Shopov, D. Y., Mercado, B. Q., Balcells, D., Brudvig, G. W., & Crabtree, R. H. (2017). Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand. Angewandte Chemie - International Edition, 56(42), 13047-13051. https://doi.org/10.1002/anie.201707593

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 journalArticle

Sharninghausen, LS, Sinha, SB, Shopov, DY, Mercado, BQ, Balcells, D, Brudvig, GW & Crabtree, RH 2017, 'Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand', Angewandte Chemie - International Edition, vol. 56, no. 42, pp. 13047-13051. https://doi.org/10.1002/anie.201707593
Sharninghausen, Liam S. ; Sinha, Shashi Bhushan ; Shopov, Dimitar Y. ; Mercado, Brandon Q. ; Balcells, David ; Brudvig, Gary W ; Crabtree, Robert H. / Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O-Donor Organic Ligand. In: Angewandte Chemie - International Edition. 2017 ; Vol. 56, No. 42. pp. 13047-13051.
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