{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T03:17:24Z","timestamp":1785813444336,"version":"3.56.0"},"reference-count":59,"publisher":"Wiley","issue":"39","license":[{"start":{"date-parts":[[2017,8,25]],"date-time":"2017-08-25T00:00:00Z","timestamp":1503619200000},"content-version":"am","delay-in-days":365,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2016,8,25]],"date-time":"2016-08-25T00:00:00Z","timestamp":1472083200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000002","name":"National Institutes of Health","doi-asserted-by":"publisher","award":["GM-070757"],"award-info":[{"award-number":["GM-070757"]}],"id":[{"id":"10.13039\/100000002","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2016,9,19]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Given the importance of Fe\u2013NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein a redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand is described. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark\u2013Feltham numbers: {FeNO}<jats:sup>8<\/jats:sup>, {FeNO}<jats:sup>9<\/jats:sup>, and {FeNO}<jats:sup>10<\/jats:sup>. These {FeNO}<jats:sup>8\u201310<\/jats:sup> compounds are each low\u2010spin, and feature linear yet strongly activated nitric oxide ligands. Use of M\u00f6ssbauer, EPR, NMR, UV\/Vis, and IR\u2005spectroscopy, in conjunction with DFT\u2005calculations, provides insight into the electronic structures of this uncommon redox series of iron nitrosyl complexes. In particular, the data collectively suggest that {TPBFeNO}<jats:sup>8\u201310<\/jats:sup> are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark\u2013Feltham numbers.<\/jats:p>","DOI":"10.1002\/anie.201605403","type":"journal-article","created":{"date-parts":[[2016,8,25]],"date-time":"2016-08-25T13:40:12Z","timestamp":1472132412000},"page":"11995-11998","source":"Crossref","is-referenced-by-count":37,"title":["A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}<sup>8\u201310<\/sup>"],"prefix":"10.1002","volume":"55","author":[{"given":"Matthew J.","family":"Chalkley","sequence":"first","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology  1200 E. California Blvd. Pasadena CA 91125 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6610-4414","authenticated-orcid":false,"given":"Jonas C.","family":"Peters","sequence":"additional","affiliation":[{"name":"Division of Chemistry and Chemical Engineering California Institute of Technology  1200 E. California Blvd. Pasadena CA 91125 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,8,25]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1152\/physrev.00029.2006"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chembiol.2011.09.009"},{"key":"e_1_2_2_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)80259-3"},{"key":"e_1_2_2_5_1","unstructured":"\u00a0"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr000074t"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1080\/02603594.2013.847828"},{"key":"e_1_2_2_8_1","unstructured":"\u00a0"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja030645"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja905062w"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2012.08.026"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic400977h"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201305291"},{"key":"e_1_2_2_13_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201305291"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201505166"},{"key":"e_1_2_2_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201505166"},{"key":"e_1_2_2_15_1","unstructured":"Enemark\u2013Feltham notation is widely used in metal nitrosyl chemistry and is determined by summing the number of metal d\u2005electrons and N\u2013O \u03c0*\u2005electrons."},{"key":"e_1_2_2_16_1","unstructured":"\u00a0"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1960-0511"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201309767"},{"key":"e_1_2_2_18_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201309767"},{"key":"e_1_2_2_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic7006556"},{"key":"e_1_2_2_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b00584"},{"key":"e_1_2_2_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201006918"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201006918"},{"key":"e_1_2_2_22_1","first-page":"4483","volume":"133","author":"Lee Y.","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"e_1_2_2_23_1","unstructured":"CCDC1481636 ({TPBFeNO}8) 1481637 ({TPBFeNO}9) and 1481638 ({TPBFeNO}10) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge fromThe Cambridge Crystallographic Data Centre."},{"key":"e_1_2_2_24_1","unstructured":"\u00a0"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2007.04.008"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja208675p"},{"key":"e_1_2_2_27_1","unstructured":"\u00a0"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201601742"},{"key":"e_1_2_2_28_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201601742"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1SC00582K"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0401242"},{"key":"e_1_2_2_31_1","unstructured":"Asymmetric quadrupole doublets in diamagnetic species can be caused by a variety of solid-state effects. We believe that to be the case here as both powdered samples and57Fe-enriched 2-MeTHF solution samples demonstrate symmetric quadrupole doublets. (See M\u00f6ssbauer section of the Supporting Information for a further discussion and additional spectra.)"},{"key":"e_1_2_2_32_1","unstructured":"\u00a0"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-540-88428-6"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b02908"},{"key":"e_1_2_2_35_1","unstructured":"\u00a0"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.660"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b03432"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b01706"},{"key":"e_1_2_2_39_1","unstructured":"As we noted in Ref.\u2005[16c] strong covalency between the metal and the TPB\u2005ligand leads to a non-classical relationship between isomer shift and redox state in these species. Low-spin complexes of these types feature low isomer shifts regardless of formal oxidation state."},{"key":"e_1_2_2_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja206042k"},{"key":"e_1_2_2_41_1","first-page":"45","volume-title":"Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine I","author":"Lewandowska H.","year":"2014"},{"key":"e_1_2_2_42_1","unstructured":"For comparison the Wiberg bond index calculation for [TPBFeN2]\u2212(isoelectronic to {TPBFeNO}9) provides an Fe\u2212B bond order of 0.5526 compared to 0.4402 and an Fe\u2212N bond order of 0.9796 compared to 1.5958."},{"key":"e_1_2_2_43_1","unstructured":"For comparison the Wiberg bond index calculation for [TPBFe(NAd)]+(isoelectronic to {TPBFeNO}9) provides an Fe\u2212B bond order of 0.2718 compared to 0.4402 and an Fe\u2212N bond order of 1.7980 compared to 1.5958."},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1016\/0021-9614(85)90037-0"},{"key":"e_1_2_2_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic50039a027"},{"key":"e_1_2_2_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic50093a003"},{"key":"e_1_2_2_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00713a079"},{"key":"e_1_2_2_48_1","unstructured":"\u00a0"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1677527"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.33.8822"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_2_52_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.463096"},{"key":"e_1_2_2_53_2","doi-asserted-by":"publisher","DOI":"10.1039\/b508541a"},{"key":"e_1_2_2_54_1","unstructured":"Broken-symmetry calculations in which anS=1\u2005NO\u2212is antiferromagnetically coupled to a metal center are often used in the case of linear M\u2013NO complexes. Attempts to optimize such wavefunctions with BP86 led to their collapse back to the low-spin wavefunction. Further DFT\u2005discussions including low-spin and broken-symmetry calculations with B3LYP can be found in the Supporting Information."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201605403","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201605403","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201605403","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201605403","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/anie.201605403","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201605403","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,24]],"date-time":"2023-08-24T01:01:48Z","timestamp":1692838908000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201605403"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2016,8,25]]},"references-count":59,"journal-issue":{"issue":"39","published-print":{"date-parts":[[2016,9,19]]}},"alternative-id":["10.1002\/anie.201605403"],"URL":"https:\/\/doi.org\/10.1002\/anie.201605403","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2016,8,25]]}}}