Boronated Cyanometallates
Brendon J McNicholas1, Cherish Nie1, Anex Jose2
1Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Pasadena, California91125, United States.
Inorganic Chemistry
|December 19, 2022
Summary
This study details novel boronated cyanometallates and metalloboratonitriles, revealing stable manganese and chromium complexes with tunable electronic properties. These findings advance the understanding of metal-cyanide-boron chemistry.
Area of Science:
- Coordination Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Cyanometallate complexes are vital in catalysis and materials science.
- Incorporating boron into metal-cyanide frameworks offers new electronic and structural possibilities.
- Understanding structure-property relationships in these novel compounds is crucial for targeted applications.
Purpose of the Study:
- To synthesize and characterize novel boronated cyanometallates and metalloboratonitriles.
- To investigate the electronic structures and spectroscopic properties of these new compounds.
- To explore the redox behavior and stability of the synthesized complexes.
Main Methods:
- Synthesis and characterization using X-ray crystallography and various spectroscopic techniques (UV-vis-NIR, NMR, IR, MCD).
- Computational analysis employing CASSCF+NEVPT2 methods for electronic structure calculations.
- Electrochemical studies (spectroelectrochemistry) and electron paramagnetic resonance (EPR) spectroscopy.
Main Results:
- Successfully synthesized and characterized thirteen boronated cyanometallates [M(CN-BR3)6]3/4/5- and one metalloboratonitrile [Cr(NC-BPh3)6]3-.
- Assigned ligand-to-metal charge-transfer (LMCT) absorptions and MCD C-terms to specific electronic transitions.
- Observed highly reversible redox couples and identified surprisingly stable Mn(I) and Cr(II) complexes with B(C6F5)3 ligands.
Conclusions:
- The study establishes a new class of boronated cyanometallate compounds with tunable electronic properties.
- The observed correlation between reduction potentials and LMCT energies highlights the influence of boron substituents.
- The stability of specific manganese and chromium complexes opens avenues for further investigation in materials science.
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