{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,18]],"date-time":"2026-04-18T08:58:52Z","timestamp":1776502732040,"version":"3.51.2"},"reference-count":22,"publisher":"American Association for the Advancement of Science (AAAS)","issue":"5813","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Science"],"published-print":{"date-parts":[[2007,2,9]]},"abstract":"<jats:p>\n                    Iron(V)-oxo species have been proposed as key reactive intermediates in the catalysis of oxygen-activating enzymes and synthetic catalysts. Here, we report the synthesis of [Fe(TAML)(O)]\n                    <jats:sup>\u2013<\/jats:sup>\n                    in nearly quantitative yield, where TAML is a macrocyclic tetraamide ligand. Mass spectrometry, Mo\u0308ssbauer, electron paramagnetic resonance, and x-ray absorption spectroscopies, as well as reactivity studies and density functional theory calculations show that this long-lived (hours at \u201360\u00b0C) intermediate is a spin\n                    <jats:italic>S<\/jats:italic>\n                    = 1\/2 iron(V)-oxo complex. Iron-TAML systems have proven to be efficient catalysts in the decomposition of numerous pollutants by hydrogen peroxide, and the species we characterized is a likely reactive intermediate in these reactions.\n                  <\/jats:p>","DOI":"10.1126\/science.1133417","type":"journal-article","created":{"date-parts":[[2006,12,21]],"date-time":"2006-12-21T20:54:56Z","timestamp":1166734496000},"page":"835-838","source":"Crossref","is-referenced-by-count":462,"title":["Chemical and Spectroscopic Evidence for an Fe\n                    <sup>V<\/sup>\n                    -Oxo Complex"],"prefix":"10.1126","volume":"315","author":[{"given":"Filipe Tiago","family":"de Oliveira","sequence":"first","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"given":"Arani","family":"Chanda","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"given":"Deboshri","family":"Banerjee","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"given":"Xiaopeng","family":"Shan","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"given":"Sujit","family":"Mondal","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"suffix":"Jr.","given":"Lawrence","family":"Que","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"given":"Emile L.","family":"Bominaar","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"given":"Eckard","family":"Mu\u0308nck","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]},{"given":"Terrence J.","family":"Collins","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA."},{"name":"Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA."}]}],"member":"221","reference":[{"key":"e_1_3_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0307143"},{"key":"e_1_3_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9900275"},{"key":"e_1_3_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020628n"},{"key":"e_1_3_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0542439"},{"key":"e_1_3_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja060048y"},{"key":"e_1_3_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200462368"},{"key":"e_1_3_2_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2005.12.016"},{"key":"e_1_3_2_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0460458"},{"key":"e_1_3_2_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200504511"},{"key":"e_1_3_2_11_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1069297"},{"key":"e_1_3_2_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)00142-8"},{"key":"e_1_3_2_13_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1119092"},{"key":"e_1_3_2_14_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.299.5609.1037"},{"key":"e_1_3_2_15_2","unstructured":"Materials and methods are available as supporting material on Science Online."},{"key":"e_1_3_2_16_2","unstructured":"The 3d spin-flip transition (d xy ) \u03b2 \u2192 (d xz ) \u03b1 is higher in energy than the ligand-to-metal transition (\u03c0 p ) \u03b2 \u2192 (d xz ) \u03b1 where \u03c0 p is the redox-active orbital of the phenyl moiety owing to the large {d xz d yz } \u2013 d xy splitting."},{"key":"e_1_3_2_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2006.01.012"},{"key":"e_1_3_2_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2006.01.013"},{"key":"e_1_3_2_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2006.01.020"},{"key":"e_1_3_2_20_2","unstructured":"The free-ion value for the one-electron spin-orbit coupling constant \u03b6 is 580 cm \u20131 ( 21 ). Given the high degree of covalency of 3 the adopted \u03b6 is not unreasonable. P = 2 g N \u03b2 \u03b2 N <r \u20133 > 3d has been taken as 50 T."},{"key":"e_1_3_2_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja062332v"},{"key":"e_1_3_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00065a010"},{"key":"e_1_3_2_23_2","unstructured":"The work was supported by NIH grants EB001475 (E.M.) and GM-38767 (L.Q.) the Heinz Endowments (T.J.C.) Environmental Protection Agency (grant RD 83 to T.J.C.) and the Heinz Foundation for the Teresa Heinz Scholars for Environmental Research award (to D.B.). XAS data were collected on beamline X3B at the National Synchrotron Light Source which is supported by the U.S. Department of Energy and the National Institutes of Health. We also thank M. Costas and A. Ghosh for valuable suggestions."}],"container-title":["Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.science.org\/doi\/pdf\/10.1126\/science.1133417","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,1,10]],"date-time":"2024-01-10T04:41:21Z","timestamp":1704861681000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.science.org\/doi\/10.1126\/science.1133417"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2007,2,9]]},"references-count":22,"journal-issue":{"issue":"5813","published-print":{"date-parts":[[2007,2,9]]}},"alternative-id":["10.1126\/science.1133417"],"URL":"https:\/\/doi.org\/10.1126\/science.1133417","relation":{"has-review":[{"id-type":"doi","id":"10.3410\/f.1066751.519673","asserted-by":"object"}]},"ISSN":["0036-8075","1095-9203"],"issn-type":[{"value":"0036-8075","type":"print"},{"value":"1095-9203","type":"electronic"}],"subject":[],"published":{"date-parts":[[2007,2,9]]}}}