Aluminum Complexes with Redox-Active Formazanate Ligand: Synthesis, Characterization, and Reduction Chemistry

The synthesis of aluminum complexes with redox-active formazanate ligands is described. Salt metathesis using AlCl3 was shown to form a five-coordinate complex with two formazanate ligands, whereas organometallic aluminum starting materials yield tetrahedral mono­(formazanate) aluminum compounds. Th...

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Bibliographic Details
Published in:Inorganic chemistry 2019-05, Vol.58 (9), p.6344-6355
Main Authors: Mondol, Ranajit, Otten, Edwin
Format: Article
Language:English
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Summary:The synthesis of aluminum complexes with redox-active formazanate ligands is described. Salt metathesis using AlCl3 was shown to form a five-coordinate complex with two formazanate ligands, whereas organometallic aluminum starting materials yield tetrahedral mono­(formazanate) aluminum compounds. The aluminum diphenyl derivative was successfully converted to the iodide complex (formazanate)­AlI2, and a comparison of spectroscopic/structural data for these new complexes is provided. Characterization by cyclic voltammetry is supplemented by chemical reduction to demonstrate that ligand-based redox reactions are accessible in these compounds. The possibility to obtain a formazanate aluminum­(I) carbenoid species by two-electron reduction was examined by experimental and computational studies, which highlight the potential impact of the nitrogen-rich formazanate ligand on the electronic structure of compounds with this ligand.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.9b00553