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It was found that the dinuclear \u03bc\u2010hydroxide complexes {[(PCN<jats:sup>R<\/jats:sup>)Pd]<jats:sub>2<\/jats:sub>(\u03bc\u2010OH)}(OTf) (PCN<jats:sup>H<\/jats:sup>=1\u2010[3\u2010[(di\u2010<jats:italic>tert<\/jats:italic>\u2010butylphosphino)methyl]phenyl]\u20101<jats:italic>H<\/jats:italic>\u2010pyrazole; PCN<jats:sup>Me<\/jats:sup>=1\u2010[3\u2010[(di\u2010<jats:italic>tert<\/jats:italic>\u2010butylphosphino)methyl]phenyl]\u20105\u2010methyl\u20101<jats:italic>H<\/jats:italic>\u2010pyrazole) react with H<jats:sub>2<\/jats:sub> to form the analogous dinuclear hydride species {[(PCN<jats:sup>R<\/jats:sup>)Pd]<jats:sub>2<\/jats:sub>(\u03bc\u2010H)}(OTf). The dinuclear \u03bc\u2010hydride complexes were fully characterized, and are rare examples of structurally characterized unsupported singly bridged \u03bc\u2010H Pd<jats:sup>II<\/jats:sup> dimers. The {[(PCN<jats:sup>Me<\/jats:sup>)Pd]<jats:sub>2<\/jats:sub>(\u03bc\u2010OH)}(OTf) hydrogenolysis mechanism was investigated through experiments and computations. The hydrogenolysis of the mononuclear complex (PCN<jats:sup>H<\/jats:sup>)Pd\u2010OH resulted in a mixed ligand dinuclear species [(PCN<jats:sup>H<\/jats:sup>)Pd](\u03bc\u2010H)[(PCC)Pd] (PCC=a dianionic version of PCN<jats:sup>H<\/jats:sup> bound through phosphorus P, aryl C, and pyrazole C atoms) generated from initial ligand \u201crollover\u201d C\u2212H activation. Further exposure to H<jats:sub>2<\/jats:sub> yields the bisphosphine Pd<jats:sup>0<\/jats:sup> complex Pd[(H)PCN<jats:sup>H<\/jats:sup>]<jats:sub>2<\/jats:sub>. When the ligand was protected at the pyrazole 5\u2010position in the (PCN<jats:sup>Me<\/jats:sup>)Pd\u2212OH complex, no hydride formed under the same conditions; the reaction proceeded directly to the bisphosphine Pd<jats:sup>0<\/jats:sup> complex Pd[(H)PCN<jats:sup>Me<\/jats:sup>]<jats:sub>2<\/jats:sub>. Reaction mechanisms for the hydrogenolysis of the monomeric and dimeric hydroxides are proposed.<\/jats:p>","DOI":"10.1002\/chem.201900507","type":"journal-article","created":{"date-parts":[[2019,5,15]],"date-time":"2019-05-15T06:56:32Z","timestamp":1557903392000},"page":"9920-9929","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Hydrogenolysis of Dinuclear PCN<sup>R<\/sup> Ligated Pd<sup>II<\/sup> \u03bc\u2010Hydroxides and Their Mononuclear Pd<sup>II<\/sup> Hydroxide Analogues"],"prefix":"10.1002","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6526-8997","authenticated-orcid":false,"given":"Wilson D.","family":"Bailey","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Washington  Box 351700 Seattle Washington 98195-1700 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3858-1261","authenticated-orcid":false,"given":"Alexander S.","family":"Phearman","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Pennsylvania  Philadelphia PA 19104 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4407-6026","authenticated-orcid":false,"given":"Lapo","family":"Luconi","sequence":"additional","affiliation":[{"name":"Institute of Chemistry of Organometallic Compounds, ICCOM-CNR and Consorzio INSTM  Via Madonna del Piano 10-50019 Sesto Fiorentino Florence Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1283-2803","authenticated-orcid":false,"given":"Andrea","family":"Rossin","sequence":"additional","affiliation":[{"name":"Institute of Chemistry of Organometallic Compounds, ICCOM-CNR and Consorzio INSTM  Via Madonna del Piano 10-50019 Sesto Fiorentino Florence Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3906-8841","authenticated-orcid":false,"given":"Dmitry G.","family":"Yakhvarov","sequence":"additional","affiliation":[{"name":"Kazan Federal University  420008 Kazan Russian Federation"},{"name":"Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS  420008 Kazan Russian Federation"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lucia","family":"D'Accolti","sequence":"additional","affiliation":[{"name":"Universit\u00e0 di Bari \u201cA. 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