{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,15]],"date-time":"2026-07-15T04:33:45Z","timestamp":1784090025599,"version":"3.55.0"},"reference-count":15,"publisher":"Wiley","issue":"2","license":[{"start":{"date-parts":[[2023,2,22]],"date-time":"2023-02-22T00:00:00Z","timestamp":1677024000000},"content-version":"vor","delay-in-days":21,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPlusChem"],"published-print":{"date-parts":[[2023,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Reduced nucleophilicities \u0418<jats:sub>B<\/jats:sub> of axially symmetric molecules B were determined from \n<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cplu202300032-gra-0903.png\" xlink:title=\"image\"\/>, where <jats:italic>D<\/jats:italic><jats:sub>e<\/jats:sub> is the equilibrium dissociation energy of the complexes B\u22c5\u22c5\u22c5XY, <jats:italic>N<\/jats:italic><jats:sub>B<\/jats:sub> is the nucleophilicity of B, <jats:italic>E<\/jats:italic><jats:sub>XY<\/jats:sub> is the electrophilicity of the halogen\u2010bond donor XY and <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cplu202300032-math-0001.png\" xlink:title=\"urn:x-wiley:21926506:media:cplu202300032:cplu202300032-math-0001\"\/>\n is the minimum electrostatic surface potential of B. The series B\u22c5\u22c5\u22c5ClY, B\u22c5\u22c5\u22c5BrY, B\u22c5\u22c5\u22c5IY (Y=F, Cl, Br, I, CN, and CCH) as well as (B\u22c5\u22c5\u22c5XY, XY=F<jats:sub>2<\/jats:sub>, Cl<jats:sub>2<\/jats:sub>, Br<jats:sub>2<\/jats:sub>,and BrCl) of complexes were investigated. Molecules B were grouped so that the terminal atom involved in the halogen bond was fixed within the group. Groups having N as the terminal atom were RCN (R=CH<jats:sub>3<\/jats:sub>, H, and F) or RN (R=N and P), those with C as the terminal atom were RNC (R=H and F) and RC (R=O, S and Se), and those with a terminal O atom were R=C=O (R=O or S). Graphs of <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cplu202300032-math-0002.png\" xlink:title=\"urn:x-wiley:21926506:media:cplu202300032:cplu202300032-math-0002\"\/>\n versus <jats:italic>E<\/jats:italic><jats:sub>XY<\/jats:sub> for each group were straight lines through the origin, with generally different gradients, hence implying different <jats:italic>N<\/jats:italic><jats:sub>B<\/jats:sub>. By contrast, when <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cplu202300032-math-0003.png\" xlink:title=\"urn:x-wiley:21926506:media:cplu202300032:cplu202300032-math-0003\"\/>\n was the ordinate the lines conflated to give a single straight line, which then defines a common (reduced) nucleophilicity \u0418<jats:sub>B<\/jats:sub> for that group of B. Hence it was concluded that \u0418<jats:sub>B<\/jats:sub> is an intrinsic property of the terminal atom, independent of the remainder of B, and only weakly dependent on the type (C, N or O) of the terminal atom. Moreover, \u0418<jats:sub>B<\/jats:sub> for each B was the same as determined previously from the hydrogen\u2010bonded series B\u22c5\u22c5\u22c5HX, (X=F, Cl, Br, I, CN, CCH, and CP).<\/jats:p>","DOI":"10.1002\/cplu.202300032","type":"journal-article","created":{"date-parts":[[2023,2,6]],"date-time":"2023-02-06T06:29:16Z","timestamp":1675664956000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Reduced Nucleophilicities \u0418<sub>B<\/sub> of Lewis Bases B: Is \u0418<sub>B<\/sub> Independent of Whether B is Involved in a Hydrogen Bond or a Halogen Bond?"],"prefix":"10.1002","volume":"88","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6876-6211","authenticated-orcid":false,"given":"Ibon","family":"Alkorta","sequence":"first","affiliation":[{"name":"Instituto de Qu\u00edmica M\u00e9dica (IQM-CSIC)  Juan de la Cierva, 3 28006 Madrid Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3468-9865","authenticated-orcid":false,"given":"Anthony","family":"Legon","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Bristol  Cantock's Close Bristol BS8 1TS UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,2,22]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules22101786"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/cplu.202100088"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CP02697B"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.3390\/inorganics9020013"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199409381"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CP00779G"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CP03999K"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp110295n"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3442368"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr200168z"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4893989"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268977000101561"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.82"},{"key":"e_1_2_8_14_1","unstructured":"M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone G.\u2005A.Petersson H. Nakatsuji et\u2005al. Gaussian 16; Revision A.03; Gaussian Inc.: Wallingford CT USA 2016."},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.22885"}],"container-title":["ChemPlusChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cplu.202300032","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/cplu.202300032","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cplu.202300032","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T04:26:08Z","timestamp":1760415968000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cplu.202300032"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,2]]},"references-count":15,"journal-issue":{"issue":"2","published-print":{"date-parts":[[2023,2]]}},"alternative-id":["10.1002\/cplu.202300032"],"URL":"https:\/\/doi.org\/10.1002\/cplu.202300032","archive":["Portico"],"relation":{},"ISSN":["2192-6506","2192-6506"],"issn-type":[{"value":"2192-6506","type":"print"},{"value":"2192-6506","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,2]]},"assertion":[{"value":"2023-01-17","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-02-22","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202300032"}}