We examined the synthetic and catalytic claims that immobilization of an Fe-PNP pincer complex (1) on an amine-modified graphene oxide support yields a useful heterogeneous catalyst for the Suzuki biaryl cross-coupling reaction. Complex 1 is not formed under the reported conditions, rather the iron sulfate heptahydrate starting material (melanterite) undergoes partial dehydration to give iron sulfate tetrahydrate (rozenite). Neither rozenite nor melanterite are catalytically competent.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
Miyaura N, Suzuki A (1995) Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem Rev 95:2457–2483
Valente C, Organ MG (2011) In: Hall DG (ed) Boronic acids. Wiley-VCH, Weinheim, pp 213–262
Garrett CE, Prasad K (2004) The art of meeting palladium specifications in active pharmaceutical ingredients produced by Pd- catalyzed reactions. Adv Synth Catal 346:889–900
Guideline on the Specification Limits for Residues of Metal Catalysts or Metal Reagents, (Doc.Ref. EMEA/CHMP/SWP/4446/2000). Committee for Medicinal Products for Human Use (CHMP); European Medicines Agency: London, Feb 2008; pp 1–34
Neely JM, Bezdek MJ, Chirik PJ (2016) Insight into transmetalation enables cobalt-catalyzed Suzuki–Miyaura cross coupling. ACS Cent Sci 2:935–942
Asghar S, Tailor SB, Elorriaga D, Bedford RB (2017) Cobalt-catalyzed Suzuki biaryl coupling of aryl halides. Angew Chem Int Ed 56:16367–16370
Duong HA, Wu W, Teo Y-Y (2017) Cobalt-catalyzed cross- coupling reactions of arylboronic esters and aryl halides. Organometallics 36:4363–4366
Tailor SB, Manzotti M, Asghar S, Rowsell BJS, Luckham SLJ, Sparkes HA, Bedford RB (2019) Revisiting claims of the iron-, cobalt-, nickel-, and copper-catalyzed suzuki biaryl cross-coupling of aryl halides with aryl boronic acids. Organometallics 38:1770–1777
Bedford RB, Hall MA, Hodges GR, Huwe M, Wilkinson MC (2009) Simple mixed Fe–Zn catalysts for the Suzuki couplings of tetraarylborates with benzyl halides and 2-halopyridines. Chem Commun 42:6430–6432
Bedford RB, Gallagher T, Pye DR, Savage W (2015) Towards iron-catalysed Suzuki Biaryl cross-coupling: unusual reactivity of 2-halobenzyl halides. Synthesis 47:1761–1765
O’Brien HM, Manzotti M, Abrams RD, Elorriaga D, Sparkes HA, Davis SA, Bedford RB (2018) Iron-catalysed substrate- directed Suzuki biaryl cross-coupling. Nat Catal 1:429–437
Kylmälä T, Valkonen A, Rissanen K, Xu Y, Franzén R (2009) Retraction notice to “trans-Tetrakis(pyridine)dichloroiron(II) as catalyst for Suzuki cross-coupling in ethanol and water”. Tetrahedron Lett 50:5692
Bézier D, Darcel C (2009) Retraction: iron-catalyzed Suzuki-Miyaura cross-coupling reaction. Adv Synth Catal 351:1732–1736
Bedford RB, Nakamura M, Gower NJ, Haddow MF, Hall MA, Huwe M, Hashimoto T, Okopie RA (2009) Iron-catalysed Suzuki coupling? A cautionary tale. Tetrahedron Lett 50:6110–6111
Kumar LM, Bhat BR (2017) Cobalt pincer complex catalyzed Suzuki-Miyaura cross coupling—a green approach. J Organomet Chem 827:41–48
Kumar LM, Ansari RM, Bhat BR (2017) Catalytic activity of Fe(II) and Cu(II) PNP pincer complexes for Suzuki coupling reaction. Appl Organomet Chem 32:e4054
Ansari RM, Bhat BR (2017) Schiff base transition metal complexes for Suzuki–Miyaura cross-coupling reaction. J Chem Sci 129:1483–1490
Ansari RM, Kumar LM, Bhat BR (2018) Air-stable cobalt(II) and nickel(II) complexes with schiff base ligand for catalyzing Suzuki–Miyaura cross-coupling reaction. Russ J Coord Chem 44:1–8
Ansari RM, Mahesh LK, Bhat BR (2018) Cobalt schiff base complexes: synthesis characterization and catalytic application in suzuki-Miyaura reaction. J Chem Eng, Chin. https://doi.org/10.1016/j.cjche.2018.05.002
Saroja A, Bhat BR (2019) Cobalt schiff base immobilized on a graphene nanosheet with N, O Linkage for cross-coupling reaction. Ind Eng Chem Res 58:590–601
Kumar LM, Mishra P, Bhat BR (2019) Fe–PNP pincer complex immobilized on graphene oxide as a catalyst for Suzuki-Miyaura coupling reactions. Catal Lett 149:1118–1124
Baur WH (1962) Zur Kristallchemie der Salzhydrate. Die Kristallstrukturen von MgSO4.4H2O (leonhardtit) und FeSO4.4H2O (rozenit). Acta Cryst 15:815–826
CCDC Search performed 11th July 2019
Glatz M, Schrōder-Holzhacker C, Bichler B, Stōger B, Mereiter K, Veiros LF, Kirchner K (2016) Synthesis and characterization of cationic dicarbonyl Fe(II) PNP pincer complexes. Monatsh Chem 147:1713–1719
Glatz M, Bichler B, Mastalir M, Stöger B, Weil M, Mereiter K, Pittenauer E, Allmaier G, Veiros LF, Kirchner K (2015) Iron(II) complexes featuring κ3- and κ2-bound PNP pincer ligands – the significance of sterics. Dalton Trans 44:281–294
Benito-Garagorri D, Wiedermann J, Pollak M, Mereiter K, Kirchner K (2007) Iron(II) complexes bearing tridentate PNP pincer-type ligands as catalysts for the selective formation of 3-hydroxyacrylates from aromatic aldehydes and ethyldiazoacetate. Organometallics 26:217–222
Glatz M, Holzhacker C, Bichler B, Mastalir M, Stöger B, Mereiter K, Weil M, Veiros LF, Mösch-Zanetti NC, Kirchner K (2015) FeII carbonyl complexes featuring small to bulky PNP pincer ligands – facile substitution of κ2 P, N-bound PNP ligands by carbon monoxide. Eur J Inorg Chem 30:5053–5065
Bichler B, Glatz M, Stöger B, Mereiter K, Veiros LF, Kirchner K (2014) An iron(II) complex featuring κ3 and labile κ2-bound PNP pincer ligands—striking differences between CH2 and NH spacers. Dalton Trans 43:14517–14519
Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814
Su H, Li Z, Huo Q, Guan J, Kan Q (2014) Immobilization of transition metal (Fe2+, Co2+, VO2+ or Cu2+) Schiff base complexes onto graphene oxide as efficient and recyclable catalysts for epoxidation of styrene. RSC Adv 4:9990–9996
Pan D, Wang S, Zhao B, Wu M, Zhang H, Wang Y, Jiao Z (2009) Li storage properties of disordered graphene nanosheets. Chem Mater 21:3136–3142
Benito-Garagorri D, Becker E, Wiedermann J, Lackner W, Pollak M, Mereiter K, Kisala J, Kirchner K (2006) Achiral and chiral transition metal complexes with modularly designed tridentate PNP pincer-type ligands based on N-heterocyclic diamines. Organometallics 25:1900–1913
We thank the Engineering and Physical Sciences Research Council (EPSRC) for provision of a PhD studentship (S.B.T.).
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Tailor, S.B., Bedford, R.B. Can Immobilization of an Inactive Iron Species Switch on Catalytic Activity in the Suzuki Reaction?. Catal Lett 150, 963–968 (2020). https://doi.org/10.1007/s10562-019-02978-2
- Heterogeneous catalysis
- Homogeneous catalysis
- Mainly organic chemicals and reactions