{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,10]],"date-time":"2026-07-10T23:36:58Z","timestamp":1783726618997,"version":"3.55.0"},"reference-count":52,"publisher":"Wiley","issue":"37","license":[{"start":{"date-parts":[[2022,5,23]],"date-time":"2022-05-23T00:00:00Z","timestamp":1653264000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001843","name":"Science and Engineering Research Board","doi-asserted-by":"publisher","award":["CRG\/2021\/001174"],"award-info":[{"award-number":["CRG\/2021\/001174"]}],"id":[{"id":"10.13039\/501100001843","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2022,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Transformations of sulfane sulfur compounds (e.\u2009g. organic polysulfides (R\u2212S<jats:sub>n<\/jats:sub>\u2212R, n&gt;2) and elemental sulfur (S<jats:sub>8<\/jats:sub>)) play pivotal roles in the biochemical landscape of sulfur, and thus supports signaling activities of H<jats:sub>2<\/jats:sub>S. Although a number of previous reports illustrate amine mediated reactions of S<jats:sub>8<\/jats:sub> and thiol (RSH) yielding R\u2212S<jats:sub>n<\/jats:sub>\u2212R, this report illustrates that a tripodal [Zn<jats:sup>II<\/jats:sup>] complex [(<jats:bold>Bn<jats:sub>3<\/jats:sub>Tren<\/jats:bold>)Zn<jats:sup>II<\/jats:sup>\u2212OH<jats:sub>2<\/jats:sub>](ClO<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>) facilitates the reactions of sulfane sulfur and thiol (RSH), thereby offering an amine\u2010free biologically relevant complementary route. UV\u2010vis monitoring of the reactions and a set of control experiments underline the definitive role of [Zn<jats:sup>II<\/jats:sup>] coordination motif in the reactions of sulfane sulfur (e.\u2009g. S<jats:sub>8<\/jats:sub> and R\u2212S<jats:sub>n<\/jats:sub>\u2212R) with RSH. Detailed investigations (UV\u2010vis, NMR, ESI\u2010MS, intermediate trapping, and TEMPO radical interference experiments) disclose the key differences in the [Zn<jats:sup>II<\/jats:sup>] versus previously known amine mediated routes. Moreover, the persulfide (RSS<jats:sup>\u2212<\/jats:sup>) trapping experiments using 1\u2010fluoro\u20102,4\u2010dinitrobenzene (F\u2010DNB) reveal the intermediacy of RSS<jats:sup>\u2212<\/jats:sup> species in the [Zn<jats:sup>II<\/jats:sup>] mediated reactions of sulfane sulfur and thiol, thereby demonstrating [Zn<jats:sup>II<\/jats:sup>] assisted persulfidation of thiol in the presence of sulfane sulfur species. Of broader impact, this study underscores the feasible influence of biologically relevant [Zn<jats:sup>II<\/jats:sup>] coordination motifs (e.\u2009g. carbonic anhydrase) on the sulfane sulfur chemistry in biology.<\/jats:p>","DOI":"10.1002\/chem.202200776","type":"journal-article","created":{"date-parts":[[2022,4,26]],"date-time":"2022-04-26T04:11:11Z","timestamp":1650946271000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Cross\u2010Talks Between Sulfane Sulfur and Thiol at a Zinc(II) Site"],"prefix":"10.1002","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4348-2148","authenticated-orcid":false,"given":"Tuhin","family":"Sahana","sequence":"first","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm)  695551 Thiruvananthapuram India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5217-0840","authenticated-orcid":false,"given":"Dhanusree C.","family":"Kakkarakkal","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm)  695551 Thiruvananthapuram India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3533-3206","authenticated-orcid":false,"given":"Subrata","family":"Kundu","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm)  695551 Thiruvananthapuram India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,5,23]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00205"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ab.2011.01.044"},{"key":"e_1_2_8_3_1","unstructured":"This report uses \u201c\u2212Sn\u2212\u201d to denote variable number of S-atoms connected as linear S\u2212S chain. We have specified the number wherever required."},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0035-1560638"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b01962"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmcl.2016.12.023"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0031-9422(01)00079-6"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cbpa.2018.08.012"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr010127m"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo01287a024"},{"key":"e_1_2_8_11_1","unstructured":"\u00a0"},{"key":"e_1_2_8_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01192a050"},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1139\/v71-047"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/es102987p"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.0c01426"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC05242J"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b01074"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic025624f"},{"key":"e_1_2_8_19_1","unstructured":"\u00a0"},{"key":"e_1_2_8_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1NJ03012D"},{"key":"e_1_2_8_21_2","first-page":"61","author":"Hossain K.","year":"2022","journal-title":"Inorg. Chem."},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00115a038"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic971564f"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0RA10507D"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(00)00381-9"},{"key":"e_1_2_8_26_1","unstructured":"As the separation of the organic polysulfides is challenging due to similar polarities the calculations for gravimetric yield of individual polysulfide was hampered. Hence we report the relative ratio instead of % yields of Bn\u2212Sn\u2212Bn."},{"key":"e_1_2_8_27_1","unstructured":"Thiols are more nucleophilic under physiological conditions as compared to that in organic solvents due to relatively more stability of the thiolate anion and presence of proximal amine moiety in the biological thiols.[14]Therefore the reaction between diallyl trisulfide and glutathione in buffers does not require any external assistance.[5]."},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1039\/tf9635901019"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00826D"},{"key":"e_1_2_8_30_1","unstructured":"The absorption feature (\u03bbmax) in the range of 400\u2013500\u2005nm is anticipated for the orange coloured recently reported crystallographically characterized organic polysulfide anions (RSn\u2212).[13]."},{"key":"e_1_2_8_31_1","unstructured":"As complex2has been used for the mass spectrometric demonstration of the mono-cationic adduct complex we have evaluated the influence of complex2in the reactivity of BnSH (2\u2005equiv.)+S8(8\u2005atom equiv). While the distribution of Bn\u2212Sn\u2212Bn products for the entries\u20055 and 8 (in Table\u20051) are slightly altered the disappearance of the unreacted thiol (BnSH) in both the cases suggests comparable reactivity of these [ZnII] complexes1and2."},{"key":"e_1_2_8_32_1","unstructured":"\u00a0"},{"key":"e_1_2_8_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200804021"},{"key":"e_1_2_8_33_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200804021"},{"key":"e_1_2_8_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200900244"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b11332"},{"key":"e_1_2_8_36_1","unstructured":"Although the interaction of RSH with the [ZnII] site in1may alternatively result in the corresponding [ZnII]-thiolate complex consistent with the1H\u2005NMR and CHNS analyses we rule out the generation of such a thiolate complex in the absence of any base."},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b02066"},{"key":"e_1_2_8_38_1","unstructured":"\u00a0"},{"key":"e_1_2_8_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201704117"},{"key":"e_1_2_8_39_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201704117"},{"key":"e_1_2_8_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b03471"},{"key":"e_1_2_8_41_1","unstructured":"The reactivity of freeBn3Trenligand in the reactions of S8+BnSH is analogous to that of Et2NH (Entry\u200511 Table\u20051). Moreover UV-vis monitoring and DMAD trapping experiments forBn3Trenmediated S8+BnSH reactions show the formation of S3\u2022\u2212radical anion. In contrast [(Bn3Tren)ZnII\u2212OH2](ClO4)2(1) mediated reactions do not lead to the formation of S3\u2022\u2212radical anion. Hence we rule out the possibility of free ligand (i.\u2009e. amine) mediated route during the reactions of complex1. Furthermore perchlorate anion mediated nucleophilic activation route is excluded due to the trace yields of Bn\u2212Sn\u2212Bn from S8+BnSH control reaction in the presence of NaClO4(Entry\u200512 Table\u20051)."},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0536670"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.0c01194"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0206263"},{"key":"e_1_2_8_45_1","unstructured":"\u00a0"},{"key":"e_1_2_8_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.9b00315"},{"key":"e_1_2_8_47_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2012.01.040"},{"key":"e_1_2_8_48_1","unstructured":"\u00a0"},{"key":"e_1_2_8_49_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201601329"},{"key":"e_1_2_8_50_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1624"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202200776","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.202200776","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202200776","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T10:24:00Z","timestamp":1760264640000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202200776"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,5,23]]},"references-count":52,"journal-issue":{"issue":"37","published-print":{"date-parts":[[2022,7]]}},"alternative-id":["10.1002\/chem.202200776"],"URL":"https:\/\/doi.org\/10.1002\/chem.202200776","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,5,23]]},"assertion":[{"value":"2022-03-11","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-05-23","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202200776"}}