Alkali Cation Effects on Redox-Active Formazanate Ligands in Iron Chemistry.

Content Provider	Semantic Scholar
Author	Broere, Daniël L. J. Mercado, Brandon Q. Bill, Eckhard Lancaster, Kyle M. Sproules, Stephen Holland, Patrick L.
Copyright Year	2018
Abstract	Noncovalent interactions of organic moieties with Lewis acidic alkali cations can greatly affect structure and reactivity. Herein, we describe the effects of interactions with alkali-metal cations within a series of reduced iron complexes bearing a redox-active formazanate ligand, in terms of structures, magnetism, spectroscopy, and reaction rates. In the absence of a crown ether to sequester the alkali cation, dimeric complexes are isolated wherein the formazanate has rearranged to form a five-membered metallacycle. The dissociation of these dimers is dependent on the binding mode and size of the alkali cation. In the dimers, the formazanate ligands are radical dianions, as shown by X-ray absorption spectroscopy, Mössbauer spectroscopy, and analysis of metrical parameters. These experimental measures are complemented by density functional theory calculations that show the spin density on the bridging ligands.
Starting Page	9580
Ending Page	9591
Page Count	12
File Format	PDF HTM / HTML
Alternate Webpage(s)	https://works.bepress.com/daniel-broere/30/download/
PubMed reference number	29629752v1
Alternate Webpage(s)	https://doi.org/10.1021/acs.inorgchem.8b00226
DOI	10.1021/acs.inorgchem.8b00226
Journal	Inorganic chemistry
Volume Number	57
Issue Number	16
Language	English
Access Restriction	Open
Subject Keyword	Acids Alkalies Cations Cations, Monovalent Crown Ethers Diagnostic radiologic examination Iron Lewis, Rat Strain Ligands Magnetism X-Ray Absorption Spectroscopy
Content Type	Text
Resource Type	Article