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Synthetic Methodology for Asymmetric Ferrocene Derived Bio-conjugate Systems via Solid Phase Resin-based Methodology
Published on: March 12, 2015
First homoleptic complexes of isocyanoferrocene
Mikhail V Barybin1, Thomas C Holovics, Stephan F Deplazes
1Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas, 66045, USA. mbarybin@ku.edu
Journal of the American Chemical Society
|November 15, 2002
Summary
Researchers synthesized air-stable isocyanoferrocene (CNFc) and its chromium complex Cr(CNFc)6. These robust compounds exhibit remarkable electronic properties, highlighting the underestimated pi-accepting potential of ferrocenyl groups in organometallic chemistry.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Materials Science
Background:
- Ferrocene derivatives are versatile building blocks in coordination chemistry.
- Isocyanide ligands play a crucial role in stabilizing metal complexes.
- Understanding the electronic properties of ferrocenyl substituents is key to designing novel materials.
Purpose of the Study:
- To synthesize and characterize a novel ferrocenyl isocyanide ligand (CNFc).
- To prepare and investigate the properties of the first homoleptic chromium complex with CNFc.
- To explore the electronic and electrochemical behavior of CNFc and its metal complexes.
Main Methods:
- Synthesis of isocyanoferrocene (CNFc) via formylation and dehydration of aminoferrocene.
- Preparation of the homoleptic complex Cr(CNFc)6 by reacting CNFc with bis(naphthalene)chromium(0).
- Electrochemical oxidation of Cr(CNFc)6 to its +1 and +2 oxidation states.
- Characterization using spectroscopic (NMR, IR), magnetic, structural, and electrochemical techniques.
- Density Functional Theory (DFT) analysis of CNFc's frontier molecular orbitals.
Main Results:
- High yield synthesis of air- and thermally stable isocyanoferrocene (CNFc).
- Formation of the novel homoleptic complex Cr(CNFc)6 and its oxidized forms [Cr(CNFc)6]+ and [Cr(CNFc)6]2+.
- Demonstration of the air-, light-, and thermal robustness of the Cr(CNFc)6 compounds.
- Evidence for the significant pi-accepting ability of the ferrocenyl substituent in CNFc, comparable to aryl isocyanides.
- Detailed spectroscopic, magnetic, structural, and electrochemical data provided.
Conclusions:
- Isocyanoferrocene (CNFc) is a stable ligand capable of forming robust metal complexes.
- The ferrocenyl group exhibits substantial pi-accepting character, challenging previous assumptions.
- The synthesized complexes represent a unique motif with multiple electroactive metal centers, offering potential for new electronic materials.
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