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Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Azo-triazolide bis-cyclometalated Ir(iii) complexes via cyclization of 3-cyanodiarylformazanate ligands
Ge Mu1, Zhili Wen, Judy I-Chia Wu
1University of Houston, Department of Chemistry, 3585 Cullen Blvd. Room 112, Houston, TX, USA 77204-5003. tteets@uh.edu.
Abstract:
In this work we describe the synthesis of sterically encumbered 1,5-diaryl-3-cyanoformazanate bis-cyclometalated iridium(iii) complexes, two of which undergo redox-neutral cyclization during the reaction to produce carbon-bound 2-aryl-4-arylazo-2H-1,2,3-triazolide ligands. This transformation offers a method for accessing 2-aryl-4-arylazo-2H-1,2,3-triazolide ligands, a heretofore unreported class of chelating ligands. One formazanate complex and both triazolide complexes are structurally characterized by single-crystal X-ray diffraction, with infrared spectroscopy being the primary bulk technique to distinguish the formazanate and triazolide structures. All complexes are further characterized by UV-Vis absorption spectroscopy and cyclic voltammetry, with the triazolide compounds having similar frontier orbital energies to the formazanate complexes but much less visible absorption.
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