Iron Pincer Complexes as Catalysts in Cross-coupling of Aryl Halides and Phenylboronic Acid

  • Authors

    • Lolakshi Mahesh Kumar
    • Badekai Ramachandra Bhat
    2018-09-22
    https://doi.org/10.14419/ijet.v7i4.5.20197
  • cross-coupling, PCP, Pincer complexes, Suzuki-Miyaura.

  • Pincer complexes with iron as active metal center were synthesized to study their catalytic activity in Suzuki-Miyaura coupling reactions. Tridentate pincer ligand was synthesized by the reaction of diphenylchlorophosphine with m-aminophenol and m-phenylenediamine respectively in a 2:1 ratio in the presence of triethylamine as a base and tetrahydrofuran as solvent media. The resultant ligand was complexed with FeSO4 to obtain PCP complexes, C-1 with O and N atoms in the side arms and C-2 with both N atoms in the side arms. The synthesized complexes were examined for their C-C coupling efficiency in cross-coupling between phenyl boronic acid and para substituted halobenzenes. The research study aims to provide an alternative approach to the Pd catalyzed cross coupling methods, an otherwise subjugated method to obtain cross-coupled products. Also the study implores on the effect of variation in the side arm atom relating to the donating ability of the ligand and thereby relatively affecting the coupling yield of the catalysts.

     

     

  • References

    1. [1] Morales-Morales D and Jensen CGM., The Chemistry of Pincer Compounds, Elsevier, 2011.

      [2] Rosa GR, Rosa CH, Rominger F, Dupont J & Monteiro AL (2006), A mixed NCP pincer palladacycle as catalyst precursor for the coupling of aryl halides with aryl boronic acids. Inorganica chimica acta, 359, 6, 1947–1954.

      [3] Zhang BS, Wang C, Gong JF & Song MP (2009), Facile synthesis of achiral and chiral PCN pincer palladium(II) complexes and their application in the Suzuki and copper-free Sonogashira cross-coupling reactions. Journal of Organometallic Chemistry, 694, 16, 2555-2561.

      [4] Yorke J, Sanford J, Decken A & Xia A (2010), Iminophosphinite pincer palladium complexes: Synthesis and application. Inorganica Chimica Acta, 363, 5, 961-966.

      [5] Li P, Zhou HF, Liu F, Hu ZX & Wang HX (2013), NCN palladium pincer via transmercuration. Synthesis of [2-(2-oxazoliny)-6-(2-pyridyl)] phenylpalladium(II) chloride and its catalytic activity in Suzuki coupling. Inorganic Chemistry Communications, 32, 78-81.

      [6] Kumaravel M, Kumar P & Balakrishna MS (2014), Application of bisphosphomide-palladium(II) pincer complex in Suzuki–Miyaura cross-coupling reaction under microwave irradiation. Journal of Chemical Sciences, 126, 3, 711-716.

      [7] Selander N & Szabó KJ (2011), Catalysis by Palladium Pincer Complexes. Chemical Reviews, 111, 3, 2048-2076.

      [8] Singleton JT (2003), The uses of pincer complexes in organic synthesis. Tetrahedron, 59,11, 1837-1857.

      [9] Hurtado J, Ibañez A, Rojas R & Valderrama M (2010), Palladium(II) complexes bearing the new pincer ligand 3,5-bis(indazol-2-ylmethyl)toluene; Synthesis and catalytic properties. Inorganic Chemistry Communications, 13, 9, 1025-1028.

      [10] Inamoto K, Kuroda J, Hiroya K, Noda Y, Watanabe M & Sakamoto T (2006), Synthesis and Catalytic Activity of a Pincer-Type Bis(imidazolin-2-ylidene) Nickel(II) Complex. Organometallics, 25, 12, 3095-3098.

      [11] Estudiante-Negrete F, Hernández-Ortega S & Morales-Morales D (2012), Ni(II)–POCOP pincer compound [NiCl{C10H5-2,10-(OPPh2)2}] an efficient and robust nickel catalyst for the Suzuki–Miyaura coupling reactions. Inorganica Chimica Acta, 387, 58-63.

      [12] Kumar A, Agarwal M, Singh AK & Butcher RJ (2009), Palladium(II), platinum(II), ruthenium(II) and mercury(II) complexes of potentially tridentate Schiff base ligands of (E, N, O) type (E = S, Se, Te): Synthesis, crystal structures and applications in Heck and Suzuki coupling reactions. Inorganica Chimica Acta, 362, 9, 3208-3218.

      [13] Na Y, Park S, Han SB, Han H, Ko S & Chang S (2004), Ruthenium-Catalyzed Heck-Type Olefination and Suzuki Coupling Reactions: Studies on the Nature of Catalytic Species. Journal of the American Chemical Society, 126, 1, 250-258.

      [14] Plietker B, Iron Catalysis in Organic Chemistry: Reactions and Applications, John Wiley & Sons, 2008.

      [15] Bolm C, Legros J, Le Paih J & Zani L (2004), Iron-catalyzed reactions in organic synthesis. Chemical reviews 104, 12, 6217–6254.

      [16] Enthaler S, Junge K & Beller M (2008), Sustainable Metal Catalysis with Iron: From Rust to a Rising Star? Angewandte Chemie International Edition, 47, 18, 3317-3321.

      [17] Bichler B, Holzhacker C, Stöger B, Puchberger M, Veiros L. F & Kirchner K (2013), Heterolytic Cleavage of Dihydrogen by an Iron (II) PNP Pincer Complex via Metal–Ligand Cooperation. Organometallics, 32, 15, 4114–4121.

      [18] Bhattacharya P, Krause JA & Guan H (2011), Iron Hydride Complexes Bearing Phosphinite-Based Pincer Ligands: Synthesis, Reactivity and Catalytic Application in Hydrosilylation Reactions. Organometallics, 30, 17, 4720–4729.

      [19] Feng J & Cai C (2013), An efficient synthesis of perfluoroalkenylated aryl compounds via Pincer-Pd catalyzed Heck couplings. Journal of Fluorine Chemistry, 146, 6-10.

      [20] Shagidullin RR, Shakirov IK, Nuretdinova ON, Katsyuba SA & Filippova EA (1985), Structural information content of the stretching vibration frequencies of PN and PO bonds in five-membered heterocyclic compounds. Bulletin of the Academy of Sciences of the USSR, Division of chemical science, 34, 10, 2064-2067.

      [21] Barefield EK, Busch DH & Nelson SM (1968), Iron, cobalt, and nickel complexes having anomalous magnetic moments. Quarterly Reviews, Chemical Society, 22, 4, 457-498.

  • Downloads

  • How to Cite

    Mahesh Kumar, L., & Ramachandra Bhat, B. (2018). Iron Pincer Complexes as Catalysts in Cross-coupling of Aryl Halides and Phenylboronic Acid. International Journal of Engineering & Technology, 7(4.5), 428-430. https://doi.org/10.14419/ijet.v7i4.5.20197