{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,17]],"date-time":"2025-10-17T19:57:05Z","timestamp":1760731025936,"version":"build-2065373602"},"reference-count":29,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2018,2,8]],"date-time":"2018-02-08T00:00:00Z","timestamp":1518048000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Catalysts"],"abstract":"<jats:p>For the first time, a magnetic C-scorpionate catalyst was prepared from the iron(II) complex [FeCl2{\u03ba3-HC(pz)3}] (pz = pyrazol-1-yl) and ferrite, using the sustainable mechanochemical synthetic procedure. Its catalytic activity for the cyclohexane oxidation with tert-butyl hydroperoxide (TBHP) was evaluated in different conditions, namely under microwave irradiation and under the effect of an external magnetic field. The use of such magnetic conditions significantly shifted the catalyst alcohol\/ketone selectivity, thus revealing a promising, easy new protocol for tuning selectivity in important catalytic processes.<\/jats:p>","DOI":"10.3390\/catal8020069","type":"journal-article","created":{"date-parts":[[2018,2,9]],"date-time":"2018-02-09T12:46:27Z","timestamp":1518180387000},"page":"69","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["New Trendy Magnetic C-Scorpionate Iron Catalyst and Its Performance towards Cyclohexane Oxidation"],"prefix":"10.3390","volume":"8","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4323-4328","authenticated-orcid":false,"given":"Ana","family":"Ribeiro","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5501-7913","authenticated-orcid":false,"given":"In\u00eas","family":"Matias","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4060-1057","authenticated-orcid":false,"given":"Elisabete","family":"Alegria","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"},{"name":"Departamento de Engenharia Qu\u00edmica, Instituto Superior de Engenharia de Lisboa, Instituto Polit\u00e9cnico de Lisboa, R. Conselheiro Em\u00eddio Navarro, 1959-007 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6784-6540","authenticated-orcid":false,"given":"Ana","family":"Ferraria","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica-F\u00edsica Molecular and Institute of Nanoscience and Nanotechnology, DEQ, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"given":"Ana","family":"Botelho do Rego","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica-F\u00edsica Molecular and Institute of Nanoscience and Nanotechnology, DEQ, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8323-888X","authenticated-orcid":false,"given":"Armando","family":"Pombeiro","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5403-9352","authenticated-orcid":false,"given":"Lu\u00edsa","family":"Martins","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2018,2,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1222","DOI":"10.1002\/anie.200602866","article-title":"Magnetic nanoparticles: Synthesis, protection, functionalization, and application","volume":"46","author":"Lu","year":"2007","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3428","DOI":"10.1002\/anie.200905684","article-title":"Magnetically Separable Nanocatalysts: Bridges between Homogeneous and Heterogeneous Catalysis","volume":"49","author":"Shylesh","year":"2010","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"365","DOI":"10.1002\/cctc.200900314","article-title":"Magnetic Nanomixtures: A New Perspective in Catalysis","volume":"2","author":"Zhu","year":"2010","journal-title":"ChemCatChem"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"3036","DOI":"10.1021\/cr100230z","article-title":"Magnetically Recoverable Nanocatalysts","volume":"111","author":"Polshettiwar","year":"2011","journal-title":"Chem. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2906","DOI":"10.1039\/c4gc00164h","article-title":"Magnetic nanomaterials in catalysis: Advanced catalysts for magnetic separation and beyond","volume":"16","author":"Rossi","year":"2014","journal-title":"Green Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"6949","DOI":"10.1021\/cr500134h","article-title":"Fast-Growing Field of Magnetically Recyclable Nanocatalysts","volume":"114","author":"Wang","year":"2014","journal-title":"Chem. Rev."},{"key":"ref_7","unstructured":"Bal\u00e1\u017e, P. (2008). Mechanochemistry in Nanoscience and Minerals Engineering, Springer."},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Stolle, A., and Ranu, B. (2015). Ball Milling towards Green Synthesis Applications, Projects, Challenges, Royal Society of Chemistry (RCS).","DOI":"10.1039\/9781782621980"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"557","DOI":"10.1016\/j.molcata.2016.07.015","article-title":"The influence of multiwalled carbon nanotubes and graphene oxide additives on the catalytic activity of 3d metal catalysts towards 1-phenylethanol oxidation","volume":"426","author":"Ribeiro","year":"2017","journal-title":"J. Mol. Catal. A Chem."},{"key":"ref_10","first-page":"41","article-title":"Fibers, 4 Polyamide Fibers","volume":"Volume 11","author":"Estes","year":"2011","journal-title":"Ullmann\u2019s Encyclopedia of Industrial Chemistry"},{"key":"ref_11","unstructured":"Ahmed, J., Ahuja, S., Ali, I., Anderson, C., Anderson, M.J., Arai, Y., Braglia, M., Babirad, S., Bag, D., and Bagchi, A. (2014). Kirk-Othmer Encyclopedia of Chemical Technology, Wiley & Sons."},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Chiusoli, G.P., and Maitlis, P.M. (2006). Metal-Catalysis in Industrial Organic Processes, Royal Society of Chemistry.","DOI":"10.1039\/9781847555328"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"74","DOI":"10.1016\/j.ccr.2014.01.013","article-title":"Tris(pyrazol-1yl)methane metal complexes for catalytic mild oxidative functionalizations of alkanes, alkenes and ketones","volume":"265","author":"Martins","year":"2014","journal-title":"Coord. Chem. Rev."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2236","DOI":"10.1002\/ejic.201600053","article-title":"Water-soluble C-scorpionate complexes: Catalytic and biological applications","volume":"15\u201316","author":"Martins","year":"2016","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Martins, L.M.D.R.S. (2017). C-homoscorpionate oxidation catalysts\u2014Electrochemical and catalytic activity. Catalysts, 7.","DOI":"10.3390\/catal7010012"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1499","DOI":"10.1039\/C6GC03208G","article-title":"N2O-free single-pot conversion of cyclohexane to adipic acid catalysed by an iron(II) scorpionate complex","volume":"19","author":"Ribeiro","year":"2017","journal-title":"Green Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"151","DOI":"10.1016\/j.poly.2016.10.037","article-title":"Liquid phase oxidation of xylenes catalyzed by the tripodal C-scorpionate iron(II) complex [FeCl2{\u03ba3-HC(pz)3}]","volume":"125","author":"Mendes","year":"2017","journal-title":"Polyhedron"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"706","DOI":"10.1002\/adsc.200700529","article-title":"Scorpionate vanadium, iron and copper complexes as selective catalysts for the peroxidative oxidation of cyclohexane under mild conditions","volume":"350","author":"Silva","year":"2008","journal-title":"Adv. Synth. Catal."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1016\/j.apcata.2013.05.022","article-title":"Efficient cyclohexane oxidation with hydrogen peroxide catalysed by a C-scorpionate iron(II) complex immobilized on desilicated MOR zeolite","volume":"464\u2013465","author":"Martins","year":"2013","journal-title":"Appl. Catal. A Gen."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"3847","DOI":"10.1002\/cctc.201300432","article-title":"Heterogenisation of a C-scorpionate Fe(II) complex in carbon materials for cyclohexane oxidation with hydrogen peroxide","volume":"5","author":"Martins","year":"2013","journal-title":"ChemCatChem"},{"key":"ref_21","unstructured":"Naumkin, A., Kraut-Vass, V.A., Gaarenstroom, S.W., and Powell, C.J. (2012). NIST X-ray Photoelectron Spectroscopy Database, Standard Reference Database 20, Measurement Services Division of the National Institute of Standards and Technology (NIST)."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"192","DOI":"10.1021\/acs.organomet.6b00620","article-title":"Tuning Cyclohexane Oxidation: Combination of microwave irradiation and ionic liquid with the C-scorpionate [FeCl2(Tpm)] catalyst","volume":"36","author":"Ribeiro","year":"2017","journal-title":"Organometallics"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"764","DOI":"10.1002\/poc.1824","article-title":"Trends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-diones","volume":"24","author":"Kopylovich","year":"2011","journal-title":"J. Phys. Org. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Ribeiro, A.P.C., Martins, L.M.D.R.S., Alegria, E.C.B.A., Matias, I.A.S., Duarte, T.A.G., and Pombeiro, A.J.L. (2017). Catalytic performance of Fe(II)-scorpionate complexes towards cyclohexane oxidation in organic, ionic liquid and\/or supercritical CO2 media: A comparative study. Catalysts, 7.","DOI":"10.3390\/catal7080230"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"571","DOI":"10.2174\/1570178614666170420182508","article-title":"Highly selective cyclohexane oxidation catalyzed by ferrocene in ionic liquid medium","volume":"14","author":"Martins","year":"2017","journal-title":"Lett. Org. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"758","DOI":"10.1016\/j.crci.2015.03.018","article-title":"Catalytic oxidation of cyclohexane with hydrogen peroxide and a tetracopper(II) complex in an ionic liquid","volume":"18","author":"Ribeiro","year":"2015","journal-title":"C. R. Chim."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"37","DOI":"10.1016\/j.mseb.2016.11.002","article-title":"Ferrite nanoparticles: Synthesis, characterization and applications in electronic devices","volume":"215","author":"Kefini","year":"2017","journal-title":"Mater. Sci. Eng. B"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"52","DOI":"10.1016\/j.mtchem.2017.07.002","article-title":"Simple solvent-free preparation of dispersed composites and their application as catalysts in oxidation and hydrocarboxylation of cyclohexane","volume":"5","author":"Alegria","year":"2017","journal-title":"Mater. Today Chem."},{"key":"ref_29","first-page":"1351","article-title":"Oxidations by the reagent \u201cO2\u2013H2O2\u2013vanadium derivative\u2013pyrazine-2-carboxylic acid\u201d. Part 12.1 Main features, kinetics and mechanism of alkane hydroperoxidation","volume":"2","author":"Kozlov","year":"2001","journal-title":"J. Chem. Soc. Perkin Trans."}],"container-title":["Catalysts"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4344\/8\/2\/69\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T14:54:17Z","timestamp":1760194457000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4344\/8\/2\/69"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,2,8]]},"references-count":29,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2018,2]]}},"alternative-id":["catal8020069"],"URL":"https:\/\/doi.org\/10.3390\/catal8020069","relation":{},"ISSN":["2073-4344"],"issn-type":[{"type":"electronic","value":"2073-4344"}],"subject":[],"published":{"date-parts":[[2018,2,8]]}}}