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A Novel Iron Complex for Cross-Coupling Reactions of Multiple C–Cl Bonds in Polychlorinated Solvents with Grignard Reagents

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Abstract

A novel iron(III) complex (2) of a pincer ligand [1, N2,N6-bis(2,6-diisopropylphenyl)pyridine-2,6-dicarboxamide] was developed and used for remediation of polychlorinated solvents via sp3–sp3 coupling of Grignard reagents with C–Cl bonds. The use of an iron catalyst for such coupling reactions is highly desirable due to its greener and more economical nature. Complex 2 was characterized using various spectroscopic techniques: electrospray ionization mass spectrometer (ESI-MS, m/z 575.1), cyclic voltammetry (E1/2, 0.03 V and ∆E, 0.97 V), and ultraviolet visible (UV/Vis) spectroscopic techniques. The iron(III) complex showed efficient activation of multiple C–Cl bonds and catalyzing C–C coupling of polychlorinated alkyl halides, such as dichloromethane (CH2Cl2), chloroform (CHCl3), and carbon tetrachloride (CCl4), with various Grignard reagents under ambient reaction conditions. Complex 2 showed exceptional activity with reactions approaching near completion in about 5 min. With the required catalyst loading as low as 0.2 mol%, considerably high turnover numbers (TON = 483) and turnover frequency (TOF = 5,800 h−1) were obtained. None of the products detected during the reaction contained any chlorine, indicating an efficient dechlorination method while synthesizing products of synthetic and commercial interest. Interestingly, the catalyst was capable of replacing all chlorine atoms in each polychlorinated solvent under the investigations with high conversion.

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Acknowledgments

AG would like to thank NSF EPSCoR (NSF/EPS-1003970) and Department of Energy (DE-FG3606G086072) for financial support to complete the research work. The editorial assistance of Dr. Marinelle Ringer is also acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, University of Arkansas at Little Rock, 2801 South University Avenue, Little Rock, AR, 72204, USA

    Yashraj Gartia, Sharon Pulla, Punnamchandar Ramidi, Carolina Costa Farris, Darin E. Jones & Anindya Ghosh

  2. Center for Integrative Nanotechnology Sciences, University of Arkansas at Little Rock, 2801 South University Avenue, Little Rock, AR, 72204, USA

    Zeid Nima & Alexandru S. Biris

Authors
  1. Yashraj Gartia
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  2. Sharon Pulla
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  3. Punnamchandar Ramidi
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  4. Carolina Costa Farris
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  5. Zeid Nima
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  6. Darin E. Jones
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  7. Alexandru S. Biris
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  8. Anindya Ghosh
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Corresponding author

Correspondence to Anindya Ghosh.

Additional information

Alexandru S. Biris and Anindya Ghosh contributed equally to this manuscript.

Electronic supplementary material

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10562_2012_913_MOESM1_ESM.doc

Details on synthesis of 1 and its iron complex 2, and their characterization (1H-NMR, ESI-MS, cyclic voltammetry and UV–Vis spectra) are given in the supporting data. Gas chromatograms of the reactions involving CH2Cl2 with butylmagnesium chloride, CHCl3 with butylmagnesium chloride and phenylmagnesium chloride and CCl4 with butylmagnesium chloride are also given. (DOC 3362 kb)

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Gartia, Y., Pulla, S., Ramidi, P. et al. A Novel Iron Complex for Cross-Coupling Reactions of Multiple C–Cl Bonds in Polychlorinated Solvents with Grignard Reagents. Catal Lett 142, 1397–1404 (2012). https://doi.org/10.1007/s10562-012-0913-2

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  • DOI: https://doi.org/10.1007/s10562-012-0913-2

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