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These compounds possess an unusual <jats:italic>\u03bc<\/jats:italic><jats:sub>4<\/jats:sub>\u2010<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup> coordination mode for the bridging organic fragment, enforced by the rigid and dinucleating nature of the ligand utilized. Thus, the central \u03c0 system remains unperturbed and accessible for subsequent reactivity and modification. This has been corroborated by addition of a fifth copper atom, giving rise to a pentacopper acetylide complex. This work may provide a new approach by which metal\u2010metal cooperativity can be exploited in the transformation of acetylide and diyne groups to a variety of substrates, or as a starting point for the controlled synthesis of copper(I) alkyne\u2010containing clusters.<\/jats:p>","DOI":"10.1002\/anie.202310307","type":"journal-article","created":{"date-parts":[[2023,9,14]],"date-time":"2023-09-14T13:06:10Z","timestamp":1694696770000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Tetracopper \u03c3\u2010Bound <i>\u03bc<\/i>\u2010Acetylide and \u2010Diyne Units Stabilized by a Naphthyridine\u2010based Dinucleating Ligand"],"prefix":"10.1002","volume":"62","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4467-4157","authenticated-orcid":false,"given":"Pablo","family":"R\u00edos","sequence":"first","affiliation":[{"name":"Instituto de Investigaciones Qu\u00edmicas (IIQ) Departamento de Qu\u00edmica Inorg\u00e1nica Centro de Innovaci\u00f3n en Qu\u00edmica Avanzada (ORFEO-CINQA) CSIC and Universidad de Sevilla  41092 Sevilla Spain"},{"name":"Department of Chemistry University of California  Berkeley USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8745-2418","authenticated-orcid":false,"given":"Matthew S.","family":"See","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of California  Berkeley USA"},{"name":"Chemical Sciences Division Lawrence Berkeley National Laboratory  Berkeley CA 94720 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3693-1697","authenticated-orcid":false,"given":"Rex C.","family":"Handford","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of California  Berkeley USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7953-4229","authenticated-orcid":false,"given":"Jason K.","family":"Cooper","sequence":"additional","affiliation":[{"name":"Chemical Sciences Division Lawrence Berkeley National Laboratory  Berkeley CA 94720 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6671-9099","authenticated-orcid":false,"given":"T.","family":"Don Tilley","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of California  Berkeley USA"},{"name":"Chemical Sciences Division Lawrence Berkeley National Laboratory  Berkeley CA 94720 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,9,27]]},"reference":[{"unstructured":"\u00a0","key":"e_1_2_7_1_1"},{"doi-asserted-by":"publisher","key":"e_1_2_7_2_2","DOI":"10.1021\/ar0000758"},{"doi-asserted-by":"publisher","key":"e_1_2_7_3_2","DOI":"10.1016\/j.ccr.2021.214315"},{"doi-asserted-by":"publisher","key":"e_1_2_7_4_1","DOI":"10.1021\/om300628g"},{"doi-asserted-by":"publisher","key":"e_1_2_7_5_1","DOI":"10.1016\/j.ccr.2010.07.004"},{"doi-asserted-by":"publisher","key":"e_1_2_7_6_1","DOI":"10.1002\/chem.202101932"},{"doi-asserted-by":"publisher","key":"e_1_2_7_7_1","DOI":"10.1002\/anie.201708760"},{"doi-asserted-by":"publisher","key":"e_1_2_7_8_1","DOI":"10.1002\/anie.199611001"},{"doi-asserted-by":"publisher","key":"e_1_2_7_9_1","DOI":"10.1039\/b301842c"},{"doi-asserted-by":"publisher","key":"e_1_2_7_10_1","DOI":"10.1039\/b102717b"},{"doi-asserted-by":"publisher","key":"e_1_2_7_11_1","DOI":"10.1021\/acs.accounts.0c00382"},{"doi-asserted-by":"publisher","key":"e_1_2_7_12_1","DOI":"10.1039\/D2SC00848C"},{"doi-asserted-by":"publisher","key":"e_1_2_7_13_1","DOI":"10.1021\/jacs.1c02235"},{"doi-asserted-by":"publisher","key":"e_1_2_7_14_1","DOI":"10.1002\/anie.202004346"},{"doi-asserted-by":"publisher","key":"e_1_2_7_15_1","DOI":"10.1021\/jacs.6b13261"},{"doi-asserted-by":"publisher","key":"e_1_2_7_16_1","DOI":"10.1039\/b801115j"},{"unstructured":"\u00a0","key":"e_1_2_7_17_1"},{"doi-asserted-by":"publisher","key":"e_1_2_7_18_2","DOI":"10.1021\/om00007a061"},{"doi-asserted-by":"publisher","key":"e_1_2_7_19_2","DOI":"10.1021\/om100824q"},{"doi-asserted-by":"publisher","key":"e_1_2_7_20_1","DOI":"10.1002\/chem.201900332"},{"doi-asserted-by":"publisher","key":"e_1_2_7_21_1","DOI":"10.1021\/ol702758f"},{"doi-asserted-by":"publisher","key":"e_1_2_7_22_1","DOI":"10.1039\/D0SC06543A"},{"unstructured":"For experimental C\u2261C bond length values determined in the gas phase see","key":"e_1_2_7_23_1"},{"doi-asserted-by":"publisher","key":"e_1_2_7_24_2","DOI":"10.1063\/1.3553203"},{"doi-asserted-by":"publisher","key":"e_1_2_7_25_2","DOI":"10.1107\/S0108768192004774"},{"unstructured":"The calculations were performed with the Gaussian 09 program: Gaussian 09 Revision E.01 Gaussian Inc. 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