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Whereas cluster assembly with carbonylmetalates is well precedented, the use of the corresponding polyarene transition metal anions is underexplored, despite recognition of these highly reactive fragments as storable sources of atomic M<jats:sup>n\u2212<\/jats:sup>. Our application of this strategy provides structurally unique early\u2010late bimetallic species. These complexes incorporate bridging hydride ligands during their syntheses, the origin of which is elucidated via detailed isotopic labelling studies. Modification of ancillary ligand sterics and electronics alters the mechanism of bimetallic assembly; a trinuclear complex resulting from dinuclear C\u2212H activation is demonstrated as an intermediate <jats:italic>en route<\/jats:italic> to formation of the bimetallic. Further validating the promise of this rational, bottom\u2010up approach, a unique tetranuclear species was synthesized, featuring a Ta centre bearing three Ta\u2212Cu interactions.<\/jats:p>","DOI":"10.1002\/anie.202311721","type":"journal-article","created":{"date-parts":[[2023,10,13]],"date-time":"2023-10-13T16:10:25Z","timestamp":1697213425000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Accessing Ta\/Cu Architectures via Metal\u2010Metal Salt Metatheses: Heterobimetallic C\u2212H Bond Activation Affords \u03bc\u2010Hydrides"],"prefix":"10.1002","volume":"62","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2848-5244","authenticated-orcid":false,"given":"Michela L.","family":"Maiola","sequence":"first","affiliation":[{"name":"Willard Henry Dow Laboratory Department of Chemistry University of Michigan  930\u2005N. 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