{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,19]],"date-time":"2026-10-19T13:39:53Z","timestamp":1792417193389,"version":"4.4.0"},"reference-count":50,"publisher":"American Chemical Society (ACS)","issue":"41","license":[{"start":{"date-parts":[[2026,9,14]],"date-time":"2026-09-14T00:00:00Z","timestamp":1789344000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006087","name":"Direcci?n General de Asuntos del Personal Acad?mico, Universidad Nacional Aut?noma de M?xico","doi-asserted-by":"publisher","award":["LANCAD-UNAM-DGTIC-372"],"award-info":[{"award-number":["LANCAD-UNAM-DGTIC-372"]}],"id":[{"id":"10.13039\/501100006087","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100020417","name":"Consejo Mexiquense de Ciencia y Tecnolog?a","doi-asserted-by":"publisher","award":["FICDTEM-2023-44"],"award-info":[{"award-number":["FICDTEM-2023-44"]}],"id":[{"id":"10.13039\/501100020417","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,19]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>We studied the influence of bridging chalcogen atoms (\u03bc-E; E = S, Se) on the structure and reactivity of digallium dihydroxide complexes [{MeLGa(OH)}2(\u03bc-E)] [E = S (4), Se (5); MeL = CH{CMe(NAr)}2\u2013, Ar = 2,4,6-Me3C6H2]. Compounds 4 and 5 were synthesized from MeLGaCl2 and sodium chalcogenide (Na2E) in THF-NH3(l), followed by controlled hydrolysis. For the sulfur system, the intermediates [{MeLGa(Cl)}2(\u03bc-S)] (2) and [{MeLGa(NH2)}2(\u03bc-S)] (3) were isolated and characterized, whereas the corresponding selenium derivatives proved too reactive for isolation. The reactivity of 4 and 5 toward Group 4 metal amides, M(NR2)4 (M = Ti, R = Me; M = Zr, Hf, R = Et), revealed a chalcogen effect, affording both monocyclic and spirocyclic complexes from 4, while 5 selectively yielded spirocyclic complexes. Likewise, the milder amide Me2Si(NMe2)2 reacted exclusively with 5 to produce a siloxide-bridged derivative. Distinct borane-dependent pathways were also observed. Treatment of 4 and 5 with BH3\u00b7THF resulted in the Ga\u2013OH protonolysis to form cyclic borates, whereas BH3\u00b7SMe2 promoted hydride attack at gallium, yielding gallium hydrides. These results provide an insight into the ambiphilic character of 4 and 5 and establish chalcogen bridging as a strategy for tuning their bonding and reactivity.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c03433","type":"journal-article","created":{"date-parts":[[2026,9,14]],"date-time":"2026-09-14T06:02:14Z","timestamp":1789365734000},"page":"24295-24307","source":"Crossref","is-referenced-by-count":0,"title":["Tailoring\nReactivity of Molecular Gallium Hydroxides\nvia Chalcogen Bridging"],"prefix":"10.1021","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0135-3548","authenticated-orcid":true,"given":"Erandi","family":"Bernabe\u0301-Pablo","sequence":"first","affiliation":[{"name":"Universidad Nacional Auto\u0301noma de Me\u0301xico, Instituto de Qui\u0301mica , Ciudad Universitaria , ,","place":["Ciudad de Me\u0301xico, Me\u0301xico, 04510"]},{"name":"Centro Conjunto de Investigacio\u0301n en Qui\u0301micaSustentable UAEM-UNAM , Carretera Toluca-Atlacomulco Km 14.5 , 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Go\u0308ttingen , , Tammannstrasse 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Uvaldo","family":"Herna\u0301ndez-Balderas","sequence":"additional","affiliation":[{"name":"Universidad Nacional Auto\u0301noma de Me\u0301xico, Instituto de Qui\u0301mica , Ciudad Universitaria , ,","place":["Ciudad de Me\u0301xico, Me\u0301xico, 04510"]},{"name":"Centro Conjunto de Investigacio\u0301n en Qui\u0301micaSustentable UAEM-UNAM , Carretera Toluca-Atlacomulco Km 14.5 , , ,","place":["Toluca, Estado de Me\u0301xico, Me\u0301xico, 50200"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4392-5751","authenticated-orcid":true,"given":"Dietmar","family":"Stalke","sequence":"additional","affiliation":[{"name":"Georg-August Universita\u0308t Go\u0308ttingen , , Tammannstrasse 4 , ,","place":["Go\u0308ttingen, Germany, 37077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5531-7799","authenticated-orcid":true,"given":"Mo\u0301nica","family":"Moya-Cabrera","sequence":"additional","affiliation":[{"name":"Universidad Nacional Auto\u0301noma de Me\u0301xico, Instituto de Qui\u0301mica , Ciudad Universitaria , ,","place":["Ciudad de Me\u0301xico, Me\u0301xico, 04510"]},{"name":"Centro Conjunto de Investigacio\u0301n en Qui\u0301micaSustentable UAEM-UNAM , Carretera Toluca-Atlacomulco Km 14.5 , , ,","place":["Toluca, Estado de Me\u0301xico, Me\u0301xico, 50200"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,14]]},"reference":[{"key":"2026101908275360100_cit1","doi-asserted-by":"publisher","first-page":"2509","DOI":"10.1002\/cctc.201800045","article-title":"Recent Developments\non the Use of Group 13 Metal Complexes\nin 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Chem."},{"key":"2026101908275360100_cit24","doi-asserted-by":"publisher","first-page":"2895","DOI":"10.1002\/anie.200605081","article-title":"Preparation\nof Molecular Alumoxane Hydrides, Hydroxides, and Hydrogensulfides","volume":"46","author":"Gonza\u0301lez-Gallardo","year":"2007","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026101908275360100_cit25","doi-asserted-by":"publisher","first-page":"2849","DOI":"10.1002\/ejic.201300108","article-title":"Molecular Heterobimetallic Aluminoxanes\nand Aluminoxane Sulfides Containing Group 4 Metals","volume":"2013","author":"Hidalgo-Bonilla","year":"2013","journal-title":"Eur. J. Inorg. 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Soc., Dalton Trans."},{"key":"2026101908275360100_cit28","doi-asserted-by":"publisher","first-page":"2492","DOI":"10.1021\/ic970208u","article-title":"Terminal Chalcogenido Complexes of Gallium Supported\nby Tris(3,5-di-tert-butylpyrazolyl)hydroborato Ligation:\n[TpBut2]GaE (E = Se, Te)","volume":"36","author":"Kuchta","year":"1997","journal-title":"Inorg.\nChem."},{"key":"2026101908275360100_cit29","doi-asserted-by":"publisher","first-page":"210","DOI":"10.1039\/c0sc00145g","article-title":"Tris(2-mercapto-1-tert-butylimidazolyl)hydroborato\nGallium Derivatives: Synthesis of di- and triGallium Compounds in\na Sulfur-rich Coordination Environment","volume":"1","author":"Yurkerwich","year":"2010","journal-title":"Chem.\nSci."},{"key":"2026101908275360100_cit30","doi-asserted-by":"publisher","first-page":"2474","DOI":"10.1021\/ic015506c","article-title":"Dimeric\nGallium Oxide and Sulfide Species Stabilized\nby a Sterically Encumbered \u03b2-Diketiminate Ligand","volume":"40","author":"Hardman","year":"2001","journal-title":"Inorg. 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