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Guilty, innocent, or just molecules doing their thing? Structural, spectroscopic, and reactivity studies of iridium complexes with redox-active ligands

Lancaster, Kyle M. and Morsing, Thorbjorn J. and Brock-Nannestad, Theis and Palmer, Joshua H. and Bendix, Jesper (2014) Guilty, innocent, or just molecules doing their thing? Structural, spectroscopic, and reactivity studies of iridium complexes with redox-active ligands. Abstracts of Papers of the American Chemical Society, 248 . 435-INOR. ISSN 0065-7727 . http://resolver.caltech.edu/CaltechAUTHORS:20150324-081908321

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Abstract

Advances in inorg. spectroscopy and theor. methods have spurred reevaluation of the electronic structures of many compds. comprising the canon of coordination chem. X-ray absorption (XAS) and ESR (EPR) spectroscopies, in concert with d. functional theory (DFT) calcns., have been of particular value in demonstrating that many classic ligands, such as 2, 2'-bipyridine, are redox-active. Such studies are less straightforward when directed at systems in which late, third-row metals are coordinated. This lecture will discuss electronic structure studies of [tris-(penatfluorophenylcorrole)]iridium bis-pyridine complexes and trismaleonitridiledithialato iridium complexes. Their electronic structures and redox chem. will be compared to cobalt and rhodium congeners. From these studies we affirm that, with high-valent iridium, covalency is the rule and thus redox is mol. - partitioning of redox events as "ligand-centered" or "metal-centered" inaccurately describes these systems.


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Additional Information:© 2014 American Chemical Society.
Record Number:CaltechAUTHORS:20150324-081908321
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150324-081908321
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55998
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 Mar 2015 15:40
Last Modified:24 Mar 2015 15:40

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