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Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
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Three-coordinate nickel carbene complexes and their one-electron oxidation products
Vlad M Iluc1, Gregory L Hillhouse
1Gordon Center for Integrative Science, Department of Chemistry, The University of Chicago , Chicago, Illinois 60637, United States.
Journal of the American Chemical Society
|April 11, 2014
Summary
Two new nickel carbene complexes were synthesized and characterized. Their distinct reactivity upon oxidation reveals differences in electronic structure, impacting their stability and rearrangement pathways.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Carbene Complexes
Background:
- Nickel carbene complexes are crucial intermediates in various catalytic processes.
- Understanding their electronic structure and reactivity is key to designing new catalysts.
- The influence of phosphine ligands on carbene complex stability and reaction pathways requires further investigation.
Purpose of the Study:
- To synthesize and characterize two novel nickel carbene complexes with different phosphine ligands.
- To investigate the impact of ligand structure on the electronic properties and reactivity of these carbene complexes.
- To explore the oxidation behavior and stability of the synthesized nickel carbene complexes.
Main Methods:
- Photolysis of side-bound diazoalkane complexes to generate carbene complexes.
- X-ray crystallography for structural characterization.
- Electrochemical studies (1-electron oxidation) to probe reactivity and stability.
Main Results:
- Successful synthesis and characterization of two new nickel carbene complexes, (dtbpe)Ni═CH(dmp) and (dippn)Ni═CH(dmp).
- Complexes exhibited short Ni-C distances and intermediate Ni-C-C angles.
- Differential reactivity towards 1-electron oxidation: one complex rearranged to a nickel(I) alkyl, while the other formed a stable nickel(III) carbene complex.
- Oxidation and reduction processes were found to be chemically reversible.
Conclusions:
- The electronic properties and steric bulk of the phosphine ligands significantly influence the reactivity and stability of nickel carbene complexes.
- The observed differences in oxidation pathways highlight the tunability of these complexes for specific applications.
- These findings contribute to a deeper understanding of nickel carbene chemistry and its potential in catalysis.
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