Dinitrogen Activation Upon Reduction of a Triiron(II) Complex†
Yousoon Lee
Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorForrest T. Sloane
Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorDr. Geneviève Blondin
Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
CNRS, UMR 5249, LCBM, F-38054 Grenoble (France)
CEA, DSV, iRTSV, LCBM, pmb F-38054 Grenoble (France)
Search for more papers by this authorDr. Khalil A. Abboud
Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorCorresponding Author
Dr. Ricardo García-Serres
Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
CNRS, UMR 5249, LCBM, F-38054 Grenoble (France)
CEA, DSV, iRTSV, LCBM, pmb F-38054 Grenoble (France)
Ricardo García-Serres, Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
Leslie J. Murray, Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Leslie J. Murray
Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Ricardo García-Serres, Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
Leslie J. Murray, Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorYousoon Lee
Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorForrest T. Sloane
Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorDr. Geneviève Blondin
Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
CNRS, UMR 5249, LCBM, F-38054 Grenoble (France)
CEA, DSV, iRTSV, LCBM, pmb F-38054 Grenoble (France)
Search for more papers by this authorDr. Khalil A. Abboud
Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorCorresponding Author
Dr. Ricardo García-Serres
Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
CNRS, UMR 5249, LCBM, F-38054 Grenoble (France)
CEA, DSV, iRTSV, LCBM, pmb F-38054 Grenoble (France)
Ricardo García-Serres, Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
Leslie J. Murray, Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Leslie J. Murray
Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Ricardo García-Serres, Université Grenoble Alpes, LCBM, F-38054 Grenoble (France)
Leslie J. Murray, Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA)
Search for more papers by this authorL.J.M.: University of Florida and ACS Petroleum Research Fund (ACS-PRF 52704-DNI3), an NSF departmental instrumentation award (CHE-1048604); HT. K.A.A.: NSF (CHE-0821346) and UF for funding X-ray equipment purchase. R.G.S.: Labex ARCANE (ANR-11-LABX-0003-01).
Abstract
Reaction of a trinuclear iron(II) complex, Fe3Br3L (1), with KC8 under N2 leads to dinitrogen activation products (2) from which Fe3(NH)3L (2-1; L is a cyclophane bridged by three β-diketiminate arms) was characterized by X-ray crystallography. 1H NMR spectra of the protonolysis product of 2 synthesized under 14N2 and 15N2 confirm atmospheric N2 reduction, and ammonia is detected by the indophenol assay (yield ∼30 %). IR and Mössbauer spectroscopy, and elemental analysis on 2 and 2-1 as well as the tri(amido)triiron(II) 3 and tri(methoxo)triiron 4 congeners support our assignment of the reduction product as containing protonated N-atom bridges.
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