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Published on: November 28, 2016
[Cr(N)Cl4]2-: a simple nitrido complex synthesized by nitrogen-atom transfer.
1Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100, Denmark. bendix@kiku.dk
Journal of the American Chemical Society
|October 30, 2003
Summary
Researchers developed a new method to synthesize chromium(V) nitrido complexes. This approach yielded the simplest first-row transition metal nitrido complex, [Cr(N)Cl4]2-, offering insights into its electronic structure and stability.
Area of Science:
- Inorganic Chemistry
- Coordination Chemistry
- Transition Metal Chemistry
Background:
- Chromium nitrido complexes are important in inorganic chemistry.
- Previous synthesis routes for such complexes were limited.
Purpose of the Study:
- To present a new general route for synthesizing chromium(V) nitrido complexes.
- To synthesize and characterize the simplest first-row transition metal nitrido complex.
Main Methods:
- Nitrogen-atom transfer from Mn(N)(salen) to CrCl3(THF)3.
- Isolation and crystallographic analysis of the product, [Cr(N)Cl4]2-.
- Spectroscopic analysis to determine the electronic structure.
Main Results:
- Successfully synthesized the simplest first-row transition metal nitrido complex, [Cr(N)Cl4]2-.
- Determined the crystal structure, including bond lengths (Cr-N: 1.555(19) Å) and angles.
- Characterized an extreme orbital splitting scheme with a significantly lowered dx2-y2 orbital.
- Observed preservation of the {CrN}2+ moiety upon hydrolysis.
Conclusions:
- The new nitrogen-atom transfer method is effective for synthesizing chromium nitrido complexes.
- The electronic structure of [Cr(N)Cl4]2- is unique due to significant pi-bonding interactions.
- The {CrN}2+ core exhibits notable stability towards hydrolysis.
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