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Redox Activity of Oxo-Bridged Iridium Dimers in an N,O-Donor Environment: Characterization of Remarkably Stable Ir(IV,V) Complexes.

Authors :
Sinha SB
Shopov DY
Sharninghausen LS
Stein CJ
Mercado BQ
Balcells D
Pedersen TB
Reiher M
Brudvig GW
Crabtree RH
Source :
Journal of the American Chemical Society [J Am Chem Soc] 2017 Jul 19; Vol. 139 (28), pp. 9672-9683. Date of Electronic Publication: 2017 Jul 05.
Publication Year :
2017

Abstract

Chemical and electrochemical oxidation or reduction of our recently reported Ir(IV,IV) mono-μ-oxo dimers results in the formation of fully characterized Ir(IV,V) and Ir(III,III) complexes. The Ir(IV,V) dimers are unprecedented and exhibit remarkable stability under ambient conditions. This stability and modest reduction potential of 0.99 V vs NHE is in part attributed to complete charge delocalization across both Ir centers. Trends in crystallographic bond lengths and angles shed light on the structural changes accompanying oxidation and reduction. The similarity of these mono-μ-oxo dimers to our Ir "blue solution" water-oxidation catalyst gives insight into potential reactive intermediates of this structurally elusive catalyst. Additionally, a highly reactive material, proposed to be a Ir(V,V) μ-oxo species, is formed on electrochemical oxidation of the Ir(IV,V) complex in organic solvents at 1.9 V vs NHE. Spectroelectrochemistry shows reversible conversion between the Ir(IV,V) and proposed Ir(V,V) species without any degradation, highlighting the exceptional oxidation resistance of the 2-(2-pyridinyl)-2-propanolate (pyalk) ligand and robustness of these dimers. The Ir(III,III), Ir(IV,IV) and Ir(IV,V) redox states have been computationally studied both with DFT and multiconfigurational calculations. The calculations support the stability of these complexes and provide further insight into their electronic structures.

Details

Language :
English
ISSN :
1520-5126
Volume :
139
Issue :
28
Database :
MEDLINE
Journal :
Journal of the American Chemical Society
Publication Type :
Academic Journal
Accession number :
28648068
Full Text :
https://doi.org/10.1021/jacs.7b04874