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In this work, we use a combination of multinuclear (<jats:sup>17<\/jats:sup>O, <jats:sup>15<\/jats:sup>N, <jats:sup>13<\/jats:sup>C) NMR, UV\/Vis, IR spectroscopic techniques and quantum chemical computation to show unequivocally that the red\u2010violet intermediate is [Fe(CN)<jats:sub>5<\/jats:sub>N(O)S]<jats:sup>4\u2212<\/jats:sup> and the blue intermediate is [Fe(CN)<jats:sub>5<\/jats:sub>N(O)SS)]<jats:sup>4\u2212<\/jats:sup>. While the formation of [Fe(CN)<jats:sub>5<\/jats:sub>N(O)S]<jats:sup>4\u2212<\/jats:sup> has long been postulated in the literature, this study provides the most direct proof of its structure. In contrast, [Fe(CN)<jats:sub>5<\/jats:sub>N(O)SS)]<jats:sup>4\u2212<\/jats:sup> represents the first example of any metal coordination complex containing a perthionitro ligand. The new reaction pathways found in this study not only provide clues for the mode of action of nitroprusside for its pharmacological activity, but also have broader implications to the biological role of H<jats:sub>2<\/jats:sub>S, potential reactions between H<jats:sub>2<\/jats:sub>S and nitric oxide donor compounds, and the possible biological function of polysulfides.<\/jats:p>","DOI":"10.1002\/chem.201503353","type":"journal-article","created":{"date-parts":[[2015,9,28]],"date-time":"2015-09-28T05:47:20Z","timestamp":1443419240000},"page":"17172-17177","source":"Crossref","is-referenced-by-count":41,"title":["Solving the 170\u2010Year\u2010Old Mystery About Red\u2010Violet and Blue Transient Intermediates in the Gmelin Reaction"],"prefix":"10.1002","volume":"21","author":[{"given":"Yin","family":"Gao","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Abouzar","family":"Toubaei","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xianqi","family":"Kong","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gang","family":"Wu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,9,28]]},"reference":[{"key":"e_1_2_3_1_2","doi-asserted-by":"publisher","DOI":"10.1098\/rspl.1843.0200"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1098\/rstl.1849.0024"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50040a026"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)80220-9"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470166086.ch5"},{"key":"e_1_2_3_6_2","doi-asserted-by":"crossref","first-page":"211","DOI":"10.1016\/S0065-3055(08)60295-6","volume":"7","author":"Griffith W. 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