Redox Activity and Bond Activation in Iridium鈥揇iamidobenzene Complexes: A Combined Structural, (Spectro)electrochemical, and DFT Investigation

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• 作者：Margarethe van der Meer ; Sinja Manck ; Sebastian Sobottka ; Sebastian Plebst ; Biprajit Sarkar
• 刊名：Organometallics
• 出版年：2015
• 出版时间：November 23, 2015
• 年：2015
• 卷：34
• 期：22
• 页码：5393-5400
• 全文大小：472K
• ISSN：1520-6041

文摘

Noninnocent ligands are special because of their ability to act as electron reservoirs and tune reactivity at a metal center 鈥渙n-demand鈥? In the following we present two iridium(III) complexes with a diamidobenzene ligand: one that is coordinatively unsaturated and a second one that is a coordinatively saturated, regular 18 valence electron complex. We show the electrochemical interconversion between the two complexes and propose a mechanism for the same. Both the complexes have been isolated in pure forms and characterized by spectroscopic, (spectro)electrochemical, and crystallographic techniques. Additionally, results from DFT calculations are presented to decipher the bonding situation within the two complexes and to investigate the bond activation pathway leading to the interconversion of one form into another. In this work we make use of the increasingly popular concept of using redox steps at noninnocent ligands to tune bond activation and chemical reactivity at the metal center.