Desymmetrizing the ferrocene molecule
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SIRBU, Dumitru, TURTA, Constantin, BENNISTON, Andrew. Desymmetrizing the ferrocene molecule. In: Physical Methods in Coordination and Supramolecular Chemistry, 8-9 octombrie 2015, Chişinău. Chisinau, Republic of Moldova: 2015, XVIII, p. 141.
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Physical Methods in Coordination and Supramolecular Chemistry
XVIII, 2015
Conferința ""Physical Methods in Coordination and Supramolecular Chemistry""
Chişinău, Moldova, 8-9 octombrie 2015

Desymmetrizing the ferrocene molecule


Pag. 141-141

Sirbu Dumitru1, Turta Constantin1, Benniston Andrew2
 
1 Institute of Chemistry,
2 Newcastle University
 
 
Disponibil în IBN: 22 aprilie 2020


Rezumat

The first reports in 1951 by Kealy and Pauson, and later in 1952 by Miller et al., on a new organo-iron compound with the chemical formula, FeC10H10, opened up a new area of chemistry. Later in 1973 the Nobel Prize in Chemistry was awarded jointly to Fischer and Wilkinson "for their pioneering work, performed independently, on the chemistry of the organometallic, so called sandwich compounds." The so called compound ferrocene was born. Ferrocene undergoes typical aromatic reactions, such as Friedel-Crafts acetylation, alkylation, formylation, sulfonation and metalation with butyllithium, thus opening access to a wide variety of derivatives. Notably, 1,1′- and 1,2-unsymmetrical ferrocene ligands are widely studied as catalysts for organometallic cross-coupling, hydrogenations, allylic substitutions, hydroformylations, Au-, Ag-catalysed aldol reactions etc. Selective reactions on a single Cp ring to introduce two disparate functional groups (e.g., PPh2, dihydrooxazole) are possible giving planar chiral ligands. For each ring to incorporate a different functional group can be more difficult, requiring a long reaction time and a convoluted purification method. A very mild, fast and chromatography-free method to achieve a similar outcome would appear to be appealing, provided the two functional groups are useful for further reactions. The new method for desymmetrization of ferrocene molecule consists of simple oxidation with potassium permanganate of 1,1′-ferrocenedicarboxaldehyde (1), to give the desymmetrized compounds 1'-formyl-ferrocenecarboxylic acid (2) and 1'-((E)-3-oxo-but-1-enyl)ferrocenecarboxylic acid (3). These proved to be useful starting materials employed in various reactions like Michael addition and Kröhnke reactions, and as result five new compounds were obtained. The composition and structure of products was confirmed by IR, NMR, mass spectroscopies, elemental analysis and X-ray crystallography, while Mössbauer and UV-Vis absorption spectroscopies were used to study their physico-chemical properties.figureFig. 2.1. Reagents and conditions: (i) KMnO4, CH3CN/H2O, 0 °C; (ii) KMnO4, acetone/H2O, 0 °C. Acknowledgements: We thank the Engineering and Physical Sciences (EPSRC)-sponsored mass spectrometry service at Swansea for collection of mass spectra, the FP7-PEOPLE-2009-IRSES246902 grant for the exchange of researchers, EPSRC for a crystallography equipment grant, and Diamond Light Source for access to synchrotron facilities.