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Chelating tris(amidate) ligands: versatile scaffolds for nickel(II).

Matthew B Jones¹, Brian S Newell, Wesley A Hoffert

¹Department of Chemistry, Emory University, Atlanta, GA, USA. cmacbet@emory.edu.

Dalton Transactions (Cambridge, England : 2003)

|December 22, 2009

Summary

Researchers synthesized novel nickel complexes using tetradentate tris(amidate) ligands. These complexes show tunable coordination and one selectively binds cyanide, enabling the formation of unique heterobimetallic structures.

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Area of Science:

Inorganic Chemistry
Coordination Chemistry
Organometallic Chemistry

Background:

Tetradentate ligands offer versatile coordination environments for metal centers.
Nickel complexes are crucial in catalysis and materials science.
Amidate ligands provide tunable electronic and steric properties.

Purpose of the Study:

Synthesize and characterize nickel complexes with tris(amidate) ligands.
Investigate the influence of ligand substituents on nickel coordination.
Explore the cyanide binding capabilities of these nickel complexes.

Main Methods:

Synthesis of nickel-tris(amidate) complexes.
Solution-state spectroscopic methods (NMR, UV-Vis).
Single crystal X-ray diffraction analysis.
Cyanide binding studies and heterobimetallic complex assembly.
Magnetic susceptibility measurements.

Main Results:

Successfully synthesized and characterized three nickel complexes: [Ni(L(iPr))](-), [Ni(L(tBu))](-), and [Ni(L(Ph))(CH(3)CN)](-).
Demonstrated that ligand acyl substituents control nickel coordination geometry and number.
[Ni(L(iPr))](-) uniquely and irreversibly binds cyanide.
Assembled a cyanide-bridged heterobimetallic complex, [Et(4)N](3)[Ni(L(iPr))(mu(2)-CN)Co(L(iPr))].

Conclusions:

Tris(amidate) ligands provide a tunable platform for nickel coordination chemistry.
Ligand design is key to controlling metal center reactivity, including cyanide binding.
The selective cyanide binding of [Ni(L(iPr))](-) opens avenues for constructing complex multinuclear systems.